In 2004, while preparing to move to New York, Gordon successfully auditioned for the role of Martha MacKenzie in the long-running Australian soap opera Home and Away. For her portrayal of Martha, Gordon won a Logie award for "Most Popular New Female Talent" in 2006. The 2009 Logie awards saw Gordon nominated for "Most Popular Actress".

On 4 March 2007, Gordon's boyfriend of two years, Chris Burkhardt, died from acute myeloid leukemia at the age of 23. In mid 2008, a storyline was introduced into Home and Away, in which Gordon's character was diagnosed with breast cancer. Gordon drew on her experience of Burkhardt's battle with leukaemia to take on the storyline.

Gordon was a contestant on the eighth season of Dancing with the Stars. She and her partner, Stefano Oliveri, were eliminated in the fifth week, on 12 October 2008. In January 2010, it was announced that Gordon would be leaving Home and Away after almost five years. She filmed her final scenes at the end of February and they aired in June of that year. Upon leaving Home and Away, Gordon took acting lessons and attended auditions for many television shows including Cops L.A.C..

In June 2009, Gordon was discovered by police cowering in a bedroom of a flat with Mark James Judge, an alleged biker gang member, during an armed response to an alleged attempted break in. No action was taken against Gordon or Judge for making a false report. It was further alleged by some media outlets that Gordon had disclosed to police that cocaine had been consumed on the day of the incident. Gordon later apologised for the distress the incident caused. In September 2009, Gordon made her first major public appearance since the incident at a parade for Crystelle lingerie. Following the incident, Gordon broke up with her partner, media heir Ryan Stokes.

In May 2010, Gordon won her first film role in The Cup. The film, which was released in 2011, is based on Media Puzzle's win in the 2002 Melbourne Cup. Gordon plays the role of Damien Oliver's partner, Trish. In November 2010, Gordon returned to Melbourne to film her next project, Any Questions for Ben?, a Working Dog production. A Writer for the Herald Sun reported that Gordon turned down an offer to appear in a ten episode reality show series documenting the lives of the wives and girlfriends of Australian sportsmen.

In February 2011, the Actress returned to television in Network Nine's telemovie Blood Brothers, based on the Gilham family murders. Elle Halliwell of The Sunday Telegraph reported Gordon had been cast in the upcoming series of Underbelly titled Underbelly: Badness in April 2012. Gordon portrayed Kylie Keogh. In April 2016, it was announced that Gordon had been cast in the role of school Teacher Elly Conway in Neighbours. She initially signed a three-year contract and made her first appearance in July.

Gordon sold her Potts Point apartment in January 2012 for $625,000 and she then moved to Clovelly. Gordon became engaged to Sydney Roosters' Greek-Australian captain Braith Anasta in July 2011 and the couple married on 14 October 2012. On 25 August 2013, it was announced that Gordon and Anasta were expecting their first child together. Gordon gave birth to their daughter, Aleeia on 2 March 2014. Gordon and Anasta announced their separation on 11 December 2015. Gordon decided to keep her married surname, so it would be the same as her daughter's.

Gordon has been the official Celebrity ambassador and model for Australian lingerie brand Crystelle, Shoe label Tony Bianco, and swimwear label 2Chillies In 2013, she was announced as a new Myer ambassador. Gordon stepped down from ambassador duties with Myer in December 2017.