LaLiberte moved from Upstate New York to New York City at age 12 in 1993, to study ballet at the School of American Ballet. After years as a ballerina, she transitioned into modelling. She did runway shows, various shoots, appeared in the 2002 Lavazza Calendar and in magazines including Photo. She also became certified in the alternative Medicine Shiatsu and "took some other directions".

Her first screen performances were brief appearances in episodes of Law & Order: Criminal Intent and Rescue Me in 2007. In 2009, she played the lead role in the film My Normal, about a lesbian dominatrix with dreams of becoming a film maker, and had a small role in an episode of Nurse Jackie. In 2010, she starred in four films: the TV film Superego; the science fiction film Kaboom which premiered at Cannes; the comedy Dinner for Schmucks; and Paul Morrissey's drama News from Nowhere.

Her first major role came in 2011, playing the recurring role of Lulu in the second season of HBO's How to Make It in America. That year she also appeared in the drama film Shouting Secrets. In 2012, she played Arlene Schram in the seventh season of Dexter. She also appeared in another four films: the romantic comedy Wifed Out; played a lead role in Girls Against Boys; had a small role in the comedy Nous York; and starred alongside Emily Blunt, Colin Firth and Anne Heche in Arthur Newman. In 2013, she has starred in an episode of The Mentalist, reprised her role as Arlene Schram in the eighth season of Dexter and has roles in the films In a World..., written and directed by Lake Bell, and Fractured, a horror film.