By the age of twenty-two, he was already among the strongest chess players in the world. During the 1920s, he won most of the tournaments in which he played. In 1927, he became the fourth World Chess Champion by defeating Capablanca, widely considered invincible, in what would stand as the longest chess championship match held until 1985.

In the early 1930s, Alekhine dominated tournament play and won two top-class tournaments by large margins. He also played first board for France in five Chess Olympiads, winning individual prizes in each (four medals and a brillancy prize). His tournament record became more erratic from the mid-1930s onwards, and alcoholism is often blamed for his decline. Alekhine offered Capablanca a rematch on the same demanding terms that Capablanca had set for him, and negotiations dragged on for years without making much progress. Meanwhile, Alekhine defended his title with ease against Bogoljubov in 1929 and 1934. He was defeated by Euwe in 1935, but regained his crown in the 1937 rematch. His tournament record, however, remained uneven, and rising young stars like Keres, Fine, and Botvinnik threatened his title. Negotiations for a title match with Keres or Botvinnik were halted by the outbreak of World War II in Europe in 1939.

Alekhine stayed in Nazi-occupied Europe during the war, where he played in tournaments which were organised by the Nazis. Anti-Semitic articles appeared under his name, although he later claimed they were forged by the Nazis. Alekhine had good relationships with several Jewish chess players, and his fourth wife was Jewish. After the war, Alekhine was ostracized by players and tournament organizers because of the anti-Semitic articles. Negotiations with Mikhail Botvinnik for a world title match were proceeding in 1946 when Alekhine died in Portugal, in unclear circumstances.

Alekhine is known for his fierce and imaginative attacking style, combined with great positional and endgame skill. He produced innovations in a wide range of chess openings. Statistical rating systems differ about his strength relative to other players, giving him rankings between fourth and eighteenth in their "all-time" lists. Although Alekhine was declared an "enemy of the Soviet Union" after making anti-Bolshevik statements in 1927, in the 1950s he was posthumously rehabilitated and acclaimed as one of the founders of the "Soviet School of Chess", which dominated the game after World War II. He is highly regarded as a chess writer and theoretician, giving his name to Alekhine's Defence and several other opening variations, and also composed a few endgame studies. There is strong evidence that Alekhine "improved" the published scores of some of his games, although in one case he may not have been responsible for the misrepresentation.

Alekhine was born into a wealthy family in Moscow, Russia on October 31, 1892. His father Alexander Ivanovich Alekhine was a landowner and Privy Councilor to the conservative legislative Fourth Duma. His mother, Anisya Ivanovna Alekhina (born Prokhorova), was the daughter of a rich industrialist. Alekhine was first introduced to chess by his mother, an older brother, Alexei, and an older sister, Varvara (Barbara).

Alekhine's first known game was from a correspondence chess tournament that began on December 3, 1902, when he was ten years old. He participated in several correspondence tournaments, sponsored by the chess magazine Shakhmatnoe Obozrenie, in 1902–1911. In 1907, Alexander played his first over-the-board tournament, the Moscow chess club's Spring Tournament. Later that year, Alexander tied for 11th–13th in the club's Autumn Tournament; his older brother, Alexei, tied for 4th–6th place. In 1908, Alexander won the club's Spring Tournament, at the age of fifteen. In 1909, he won All-Russian Amateur Tournament in Saint Petersburg. For the next few years, he played in increasingly stronger tournaments, some of them outside Russia. At first he had mixed results, but by the age of sixteen he had established himself as one of Russia's top players. He played first board in two friendly team matches: St. Petersburg Chess Club vs. Moscow Chess Club in 1911 and Moscow vs. St. Petersburg in 1912 (both drew with Eugene Znosko-Borovsky). By the end of 1911, Alekhine moved to St. Petersburg, where he entered the Imperial Law School for Nobles. By 1912, he was the strongest chess player in the St. Petersburg Chess Society. In March 1912, he won the St. Petersburg Chess Club Winter Tournament. In April 1912, he won the 1st Category Tournament of the St. Petersburg Chess Club. In January 1914, Alekhine won his first major Russian tournament, when he tied for first place with Aron Nimzowitsch in the All-Russian Masters Tournament at St. Petersburg. Afterwards, they drew in a mini-match for first prize (they both won a game). Alekhine also played several matches in this period, and his results showed the same pattern: mixed at first but later consistently good.

In April–May 1914, another major St. Petersburg 1914 chess tournament was held in the capital of the Russian Empire, in which Alekhine took third place behind Emanuel Lasker and Jose Raul Capablanca. By some accounts, Tsar Nicholas II conferred the title of "Grandmaster of Chess" on each of the five finalists (Lasker, Capablanca, Alekhine, Tarrasch, and Marshall). Chess historian Edward Winter has questioned this, stating that the earliest known sources that support this story are an article by Robert Lewis Taylor in the June 15, 1940 issue of The New Yorker and Marshall's autobiography My 50 Years of Chess (1942). Alekhine's surprising success made him a serious contender for the World Chess Championship. Whether or not the title was formally awarded to him, "Thanks to this performance, Alekhine became a grandmaster in his own right and in the eyes of the audience." In July 1914, Alekhine tied for first with Marshall in Paris.

In July–August 1914, Alekhine was leading an international Mannheim tournament, the 19th DSB Congress (German Chess Federation Congress) in Mannheim, Germany, with nine wins, one draw and one loss, when World War I broke out. Alekhine's prize was 1,100 marks (worth about 11,000 euros in terms of purchasing power today). After the declaration of war against Russia, eleven "Russian" players (Alekhine, Bogoljubov, Bogatyrchuk, Flamberg, Koppelman, Maliutin, Rabinovich, Romanovsky, Saburov, Selezniev, Weinstein) were interned in Rastatt, Germany. In September 14, 17, and 29, 1914, four of them (Alekhine, Bogatyrchuk, Saburov, and Koppelman) were freed and allowed to return home. Alekhine made his way back to Russia (via Switzerland, Italy, London, Stockholm, and Finland) by the end of October 1914. A fifth player, Peter Romanovsky, was released in 1915, and a sixth, Flamberg, was allowed to return to Warsaw in 1916.

When Alekhine returned to Russia, he helped raise money to aid the Russian chess players who remained interned in Germany by giving simultaneous exhibitions. In December 1915, he won the Moscow Chess Club Championship. In April 1916 Alekhine won a mini-match against Alexander Evensohn with two wins and one loss at Kiev, and in summer he served in the Union of Cities (Red Cross) on the Austrian front. In September, he played five people in a blindfold display at a Russian military hospital at Tarnopol. In 1918, Alekhine won a "Triangular tournament" in Moscow. In June of the following year, Alekhine was briefly imprisoned in Odessa's death cell by the Odessa Cheka, suspected of being a spy. He was charged with links with White counter-intelligence, after the Russians liberated the Ukraine from German occupation. Rumors appeared in the West that Alekhine had been killed by the Bolsheviks.

When conditions in Russia became more settled, Alekhine proved he was among Russia's strongest players. For example, in January 1920, he swept the Moscow City Chess Championship (11/11), but was not declared Moscow Champion because he was not a resident of the city. Also in October 1920, he won the All-Russian Championship in Moscow (+9 –0 =6); this tournament was retroactively defined as the first USSR Championship. His brother Alexei took third place in the tournament for amateurs.