[6][7] Emily was scouted at the Danbury Mall when she was 10 years old by Tina Kiniry from the John Casablancas Modeling & Acting Agency of Connecticut.

Tina introduced Emily to Request Model Management in 2008 and she booked jobs as the face of Guess?

[7] In May 2009, she was signed as the face of Maybelline New York,[9] having just graduated from high school with only a few months of modeling experience,[10] and made her television commercial debut for the company's "Color Sensational Lip Color" line,[4] alongside Christy Turlington, Jessica White, and Julia Stegner.

DiDonato began modeling for Victoria's Secret in August 2009,[7] and appeared on her first magazine cover with The Block's October 2009 issue.

She has appeared in advertising campaigns for Miu Miu, Oscar de la Renta, Giorgio Armani, Calvin Klein, Trussardi, Ralph Lauren, Just Cavalli, Missoni, Elie Tahari, Longchamp, Nicole Farhi, Aldo, Gap, Juicy Couture, and Guess.