She is the daughter of Robert Schilling, a prosecutor, and Tish Schilling. She grew up in West Roxbury and Wayland, splitting time between her parents, who are divorced.
She graduated from Fordham University in 2006 with a bachelor of arts in acting. She then entered the graduate program at New York University to continue her acting studies, but left after her 2nd year.
Schilling starred in NBC's 2009 drama Mercy, where she played the lead character, Nurse Veronica Callahan, who was an Iraq war veteran. Schilling read for the part via video tape from New York City. Liz Heldens, the executive producer, and her husband were so impressed by Schilling's performance that they flew her out to Los Angeles to audition for the role. In Heldens' words "she just blew the doors off the audition".
Schilling won the Emerson College Playwright's Festival Outstanding Performance Award.
Schilling portrayed Dagny Taggart in Atlas Shrugged, the 2011 film adaptation of Ayn Rand's novel of the same name.
Schilling also recently played the female lead opposite Zac Efron in The Lucky One, a film in post-production based on the Nicholas Sparks novel of the same name.