A native of Cherry Hill, New Jersey, Ali began modeling at age 13 and traveled the world before moving to Los Angeles to study acting. Her first professional acting job was a role on the television series Nés à Chicago (1997). She received her breakthrough in the high school football drama American Boys (1999) which included her infamous whipped cream bikini scene. Roles in the horror films La maison de l'horreur (1999) and Destination finale (2000) further transitioned her career as an actress.
Acting alongside Colin Farrell, Larter starred in the Western comedy, American Outlaws (2001) which performed poorly at the box office. That year, she also starred as "Brooke Taylor Windham" in the comedy La revanche d'une blonde (2001) with Reese Witherspoon.
Not happy with how things were going, Larter moved to New York in 2002 to reassess her life and career. She reprized her role as "Clear Rivers" in the sequel Destination finale 2 (2003) for which she received star billing. A year later, she made a cameo appearance as herself on the pilot to the HBO comedy drama Entourage (2004) and starred in Kidnapping (2004) as "Isobel Delano". She had a role in 7 ans de séduction (2005) as "Gina".
Larter moved back to Los Angeles in 2006 where she auditioned for a role in the NBC sci-fi drama Heroes (2006). The pilot premiered on September 25, 2006 to successful ratings and many critics declaring it "the new Lost - Les disparus (2004)". The series ran for a total of 77 episodes in 4 Seasons when it was canceled due to diminishing ratings and high production costs. There has been interest in a mini-series or a movie to wrap up story lines.
During her time on Heroes (2006), Larter made several appearances on film. The first was the Bollywood film Marigold (2007) where she received a seven-figure salary. The movie was met with primarily negative reviews. She also starred in Resident Evil: Extinction (2007), part 3 of the popular film franchise based on the Capcom video games. She played "Claire Redfield", based on the video game character of the same name. The movie was a box office success tripling its production budget, albeit being a critical flop. Larter also appeared in the caveman comedy Homo Erectus (2007) which was released direct-to-DVD. The film co-starred Hayes MacArthur, an actor whom she was engaged to marry in December 2007.
In 2009, Larter starred opposite Beyoncé Knowles and Idris Elba in the thriller Obsessed (2009). The film opened at number one at the box office but was met with negative reviews, with some critics comparing it to Liaison fatale (1987). It was also this year that Larter and MacArthur married in a small ceremony in Maine, among the guests was Larter's close friend, Amy Smart.
She reprises her role as "Claire Redfield" in Resident Evil: Afterlife (2010), directed by Paul W.S. Anderson.
