At the Australian Open, Azarenka reached the third round of a Grand Slam singles tournament for the second consecutive time, where she lost to world No. She was upset in the first round of the French Open by Karin Knapp of Italy, and at Wimbledon, she lost in the third round to 14th-seeded Nicole Vaidišová. 1 Martina Hingis in the third round, before 2004 US Open champion Svetlana Kuznetsova beat her in the fourth round.
In mixed doubles, Azarenka and countryman Max Mirnyi won the title, defeating Meghann Shaughnessy and Leander Paes.
In doubles, Azarenka and her partner Pe'er were seeded 12th.
At the 2006 Wimbledon Championships Azarenka lost in 1st round to 2005 Junior Wimbledon and 2006 Junior French Open Champion and Wildcard Agnieszka Radwańska.
In the second round, she defeated Sorana Cîrstea of Romania, before defeating 18th-seeded and future French Open champion Francesca Schiavone of Italy in the third round.
She then lost to fourth-seeded Kuznetsova in the fourth round.
Azarenka's results at the Kremlin Cup elevated her rankings to career highs of world No. Unseeded, she reached the semifinals, where she beat fifth-seeded Shahar Pe'er of Israel, Azarenka's sixth top-20 victory. This was her first appearance as a seeded player in a Grand Slam singles tournament.
In her third career WTA tour final, she lost to Li Na, but the points she earned in this tournament were enough to improve her ranking to a career-best world No. She showed no ill effects from a leg injury while winning her first two matches, but lost in the third round to seventh-seeded, defending champion and future rival Serena Williams.