Molik started playing ITF tournaments in her native Australia in 1996 . There she won her first title in 1998, in the course of the year she had seven singles and eight doubles.
In 2005 she crowned her first final at a Grand Slam tournament with a win; together with Svetlana Kuznetsova she won the doubles competition at the Australian Open. In June 2007, she also secured the double title at the French Open , this time alongside Mara Santangelo . In total, she won five singles and seven doubles titles on the tour. She reached her highest positions in the WTA ranking with 8th place in singles and 6th place in doubles in 2005.
At the 2004 Olympic Games in Athens, she won the bronze medal in singles. She also competed for Australia in Sydney (2000) and Beijing (2008). She also played for her country in the Fed Cup from 1999 to 2010 (18 wins, 21 losses).
In September 2008, Molik announced the end of her career. But she reported back a year later with an ITF tournament win in doubles and then won three more ITF titles in singles. In 2011 she finally turned her back on the professional circus.
From 1999 to 2010 she played for the Australian Fed Cup team ; of her 39 games she was able to win 18. Alicia Molik has been the team leader since January 18, 2013.