She reached the top ten of the WTA rankings for the first time in early 2005 following her first Grand Slam quarterfinal singles appearance, at the Australian Open, where she lost 7–9 in the final set to Lindsay Davenport.

She played in the Sydney International, defeating unseeded players the entire way through the tournament before taking the title over compatriot Samantha Stosur in the final, 6–7, 6–4, 7–5.

[4] However, she defeated Mauresmo in the Tier II Qatar Ladies Open semifinals 7–6, 6–1 to set up a meeting with second seed Maria Sharapova.

As the seventh seed at the Tier I Indian Wells Open, Molik made the fourth round before losing to a returning Justine Henin in three sets.

After crashing out of the tournament in Amelia Island to Virginie Razzano, Molik took an extended break due to an inner ear infection,[6] which caused her to miss the entire clay-court season including the French Open.

Molik returned for the grass court season in Birmingham, however, lost in the second round after a first-round bye to Laura Granville.

Molik won her last match of 2005 at the tournament in Bali as the third seed, making the second round before losing to Alona Bondarenko of Ukraine.

In late 2005, Molik was diagnosed with vestibular neuronitis, an inner-ear condition caused by a virus that affected her balance, vision and energy level.

[10] Molik won her first match since returning at the 2006 French Open, reaching the third round after defeating two relative unknowns and then losing to fourth-seeded Maria Sharapova 0–6, 5–7.

[12] After these wins Molik broke back into the top 200 at 179 and played in Tokyo where she defeated Jelena Kostanić, before losing in the second round to Jamea Jackson in two sets.

Her final Australian Open warm up tournament was the Hobart International where she reached the quarterfinals, beating two higher ranked opponents on her way before losing to doubles partner Sania Mirza.

During the Australian Open, Alicia Molik won through her first- and second-round matches against rising Chinese Taipei's Chan Yung-jan, and Estonian Kaia Kanepi, before losing a three-setter against the eighth seed Patty Schnyder of Switzerland.

[13] With her impressive third-round performance, Molik improved her then-141 ranking to inside the top 100, the first time since withdrawing from numerous tournaments due to that ear infection.

[16] Molik and Santangelo, the sixth seeds in the doubles tournament, made it to the semifinals before losing to eventual champions Cara Black and Liezel Huber.

Also competing in the mixed doubles, Molik and partner Jonas Björkman made the final, before losing to Jelena Janković and Jamie Murray.

In 2008, she entered the Perth Hopman Cup where she defeated Lucie Šafářová in the first round of the round-robin competition, before losing to Sania Mirza and Serena Williams in ties involving India and the United States respectively.

Molik lost in the first round of singles qualifying at the French Open and Wimbledon in 2008, and did not win a main-draw match after January 2008.

Molik has enjoyed erratic results in doubles, where she partnered Sun Tiantian and defeated Cara Black and Liezel Huber who were the top-seeds at the tournament in Sydney.

Representing Australia alongside fellow countrywomen Sam Stosur and Casey Dellacqua, Molik was ousted in the first round by María José Martínez Sánchez 6–2, 6–2.

[21] She entered the women's doubles at the Pilot Pen Tennis event as a wildcard with Meghann Shaughnessy, losing to the Spanish duo of María José Martínez Sánchez and Nuria Llagostera Vives.

Molik then made it through to the Australian Open wildcard playoff quarterfinals after winning three out of three round-robin matches, however, suffered a shock loss to teenager Jessica Moore.

Needing more matches under her belt, Molik decided to play with compatriot Jelena Dokić in the doubles event at the same tournament.

Molik played in Australia's Fed Cup World Group II tie against Spain, however, she lost heavily in the reverse singles to Suárez Navarro 1–6, 1–6.

Molik played in Dubai, where she defeated Australian Open semifinalist and 16th seed Zheng Jie in the first round,[22] and then lost to fellow qualifier Anna-Lena Grönefeld in straight sets.