Ali Bastian joined Hollyoaks in 2001. She was involved in a controversial storyline in Hollyoaks where her character was fired from her teaching job and sent to prison after having an affair with one of her students – Justin Burton played by Chris Fountain.

At the 2006 British Soap Awards Bastian and Chris Fountain won the award for best storyline. She departed the show in 2007.

In December 2005, alongside her Hollyoaks cast mates Jodi Albert and Sarah Jayne Dunn, Bastian appeared in an exercise video called Hollyoaks Get Fit.

Bastian has also appeared on television in Jane Eyre, Cavegirl, A Touch of Frost, Twenty Four 7, and Here After.

Bastian joined ITV1 police drama The Bill as PC Sally Armstrong in summer 2007 and departed in late 2009.

She was a contestant, departing in the semi-final on Strictly Come Dancing 2009, where she was partnered with Brian Fortuna.

In week 11 Bastian severely bruised the bones of her foot while training. Doctors later gave her the all clear to go ahead and perform. There was doubt about her fitness to perform in the shows semi final. After successfully performing, Ali and Brian were eliminated, finishing in third place out of sixteen couples.

Ali holds the record for the American Smooth and the Viennese Waltz, she received a perfect score for both of these dances. The pair danced again in the Strictly Come Dancing 2009 Christmas Special, and won having again scored 40/40 for their Viennese Waltz