Along with Petrova, Kirilenko won the 2012 WTA Tour Championships in doubles and was a bronze medalist at the 2012 London Olympics.

[2] At the San Diego Open in California, Kirilenko upset second seeded Jelena Janković to advance to the quarterfinals, before losing to fellow Russian Elena Dementieva.

At the Stanford Classic in Los Angeles, she upset sixth seed Marion Bartoli in straight sets before losing to eventual champion Ana Ivanovic in the quarterfinals.

There, Kirilenko won her second WTA Tour singles title, defeating unseeded Mariya Koryttseva in straight sets.

At the Australian Open, Kirilenko reached the fourth round of a Grand Slam tournament for the first time in her career, beating sixth seed Anna Chakvetadze.

Kirilenko then reached the second round of a Tier-I event in Doha, beating Ekaterina Makarova, before losing to Anabel Medina Garrigues in three sets.

She partnered with Petrova as the second-seed doubles team and beat the top-seed pair of Hsieh Su-wei and Yaroslava Shvedova in the finals.

In the Dubai doubles tournament, Kirilenko partnered with Agnieszka Radwańska, and even though they were unseeded, they reached the final, eventually losing to Liezel Huber and Cara Black, the world No.

58, Kirilenko was unseeded at the Australian Open, where in the first round she upset her friend, former doubles partner, 2008 champion and 14th seed Maria Sharapova, 7–6, 3–6, 6–4, in a 3-hour 22-minute marathon.

She then reached the second rounds of Western & Southern Open and the Rogers Cup, losing to Vera Zvonareva and Victoria Azarenka, respectively.

At the last Premier-Mandatory event of the year, the China Open, she lost in the third round to eventual finalist and compatriot Vera Zvonareva.

In the Japan Women's Open, she retired in the second round due to a hip injury against Chang Kai-chen, after losing the first set 4–6.

She competed at the Hong Kong Tennis Classic and won the Gold Group Championship with her compatriots Vera Zvonareva and Yevgeny Kafelnikov.

[15] Seeded third at the Internationaux de Strasbourg, Kirilenko retired during her first-round match against Sloane Stephens due to a right ankle injury.

She had sudden success reaching the round of 16 for the first time with easy wins over Alexandra Cadanțu, Lourdes Domínguez Lino and Sorana Cîrstea.

[19] Playing for Russia at the Summer Olympics, Kirilenko reached the semifinal upsetting sixth seed Petra Kvitová in her quarterfinal match.

[26] In doubles, Kirilenko and Petrova upset the Williams sisters in the third round[27] before losing in the quarterfinal to eighth seeds Nuria Llagostera Vives and María José Martínez Sánchez.

Seeded second at the Korea Open, Kirilenko retired from her first-round match against Lee So-ra due to a back injury.

[35] During the Fed Cup tie versus Japan, Kirilenko played one match and beat Kimiko Date-Krumm.

[36] Seeded 12th at the Qatar Ladies Open, Kirilenko retired from her first-round match versus qualifier Ekaterina Bychkova due to a shoulder injury.

[45] Seeded sixth at the Eastbourne International, Kirilenko was suffering from a knee injury, but she still made it through to the quarterfinal where she was defeated by Yanina Wickmayer.

[46] Seeded tenth at the Wimbledon Championships, Kirilenko suffered a first-round upset at the hands of home crowd favorite Laura Robson.

[51] In Beijing at the China Open, Kirilenko lost in the third round to top seed and eventual champion Serena Williams.

[56] After missing the pair of Premier Mandatory events at Indian Wells and Miami, Kirilenko made her comeback at the Family Circle Cup in Charleston.

[63] After a month-long break, Kirilenko entered the US Open unseeded and drew fifth seed and 2006 champion Maria Sharapova in the first round.

[65] Kirilenko played her final tournament of the season at the China Open where she was defeated in the first round by qualifier Tsvetana Pironkova.

She appeared in the 2009 Sports Illustrated Swimsuit Edition alongside Daniela Hantuchová and Tatiana Golovin in a pictorial entitled "Volley of the Dolls".

[69] In November 2011, Russian ice hockey player Alexander Ovechkin of the Washington Capitals identified Kirilenko as his girlfriend on his Twitter account.

[71] In July 2014, she called off her planned wedding saying in comments distributed by the Russian Tennis Federation that there were "a lot of reasons" behind her decision.

[72] On 24 January 2015, Kirilenko married[73] Alexei Stepanov, reported to be the head of the Committee of Public Services in Moscow.