Vyalitsyna was born in the Russian city of Gorky (now Nizhny Novgorod).
Her father is a sports doctor for a football team and her mother is a pediatrician.
Vyalitsyna started her professional modeling career at the age of 15 after IMG Models scouts saw her in Saint Petersburg while looking for new faces for MTV's Fashionably Loud Europe.
She entered the contest and she won their modeling contest along with a contract with IMG Paris and, later, IMG New York.
"I've wanted to be a model ever since I was little, playing with my Barbie doll", she told The Age. "It helped (for the catwalk) that I can dance but everything is self-taught".
Within six months of her win, Vyalitsyna had worked for Anna Molinari, Chloé and Sportmax.
She has appeared on the covers of Vogue, ELLE, and Glamour.
She made her debut in the Sports Illustrated Swimsuit Issue in 2005 and has appeared in it each year since.
In February 2013, Anne Vyalitsyna dated Scottish DJ, singer-songwriter and record producer, Calvin Harris.