Valentien started out doing nude modeling for an art class in Austin. In 2009, she appeared on GodsGirls before making her porn debut for Burning Angel. Her first scene was a threesome with Mr. Pete and Alec Knight in which she engaged in anal sex. She initially used the mononym Kleio, which is the name of one of her friends, as her stage name. She decided to add a last name to it upon joining Twitter and being unable to have the usernames "Kleio" or "Kleioxxx" because they were already taken. The username "Kleio Valentine" was also taken, so she slightly changed its spelling.
Valentien lived in New York City for three years before moving to the Los Angeles metropolitan area in 2015.