Benjamin was married to Actress and singer Chiara Mastroianni from 2002 to 2005; they have a daughter, Anna, born 22 April 2003.
He wrote or performed most of the songs on the 2004 Soundtrack to Clara et Moi by Arnaud Viard, and released the album Home with his wife the same year. After two more rock oriented albums in 2005 and 2007 he was dropped by his record company and began working on his first independent release, La Superbe, released on Naïve records in 2009. This was followed by the Soundtrack album Pourquoi tu pleures in 2011 and Vengeance in 2012.
In 2012 Biolay was introduced to singer and Actress Vanessa Paradis by designer Karl Lagerfeld. They were in a relationship from 2013 to May 2015, and recorded a duet, Profite ("Enjoy"), on his album Vengeance.