Rivero was born in Argentina. She was raised in the town Cordoba, Argentina. Her mother enrolled her into a modeling school when she was a young girl. She made her modeling debut at the age of 14 at a local fashion show. An agent discovered Rivero through her modeling school at age 16 in her hometown, Cordoba. One year later, at age 17, she had a huge success when she won the "Elite Look of the Year" contest in Argentina.

She appeared in the movie The Devil Wears Prada (2006), and Boys and Girls (2000).