Away from modelling and acting, she gained critical acclaim as a singer, songwriter and musician with the release of her debut album, The Divine Comedy, featuring pop-infused traditional Ukrainian folk songs. The title was a reference to the epic poem by Dante of the same name, and was chosen by Milla after seeing a proposed cover artwork sketch by Russian artist Alexis Steele. "It had all the struggle that I'm singing about. It is the divine comedy."
She toured the US in 1994 promoting the album, and its only single, Gentlemen Who Fell, and has since performed live with her band Plastic Has Memory and written tracks for film soundtracks – but is still to release a second solo album.
She continues to write songs she describes as “demos”, provided for free download in MP3 format on her official website.
Milla and fellow model and friend Carmen Hawk launched the Jovovich-Hawk clothing line in 2003, gaining favourable attention from fashionistas. Vogue magazine praised it for its "girl-about-town cult status most designers spend years trying to achieve”. The pair mutually agreed to end the business in 2008 due to increased demands on their time. "I'm an artist. I'm not someone who can deal with shipping rates and taxes,” explained Milla.
On a personal level, Milla married Shawn Andrews in 1992 while filming Dazed and Confused together. Her mother annulled the marriage two months later: Andrews was 21 and Jovovich 16. The model then moved to Europe and met and lived with ex-bassist for Jamiroquai Stuart Zender. Back in Las Vegas in 1998, she married The Fifth Element director Luc Besson but they divorced the following year. She was also romantically linked with poet and musician Anno Birkin and Red Hot Chili Peppers guitarist John Frusciante.
Milla is known for giving a great deal of her time to charitable causes. She has served as master of ceremonies and co-chair (with Elizabeth Taylor) for the amfAR and Cinema Against AIDS event at the Venice Film Festival, and is involved with the Ovarian Cancer Research Fund and the Wildlands Project.
In March 2011, Jovovich was a guest at Mikhail Gorbachev’s 80th birthday celebration, where she sang and gave a speech thanking the former Soviet Union leader. When she and her family had left the Soviet Union in 1980, she said, they were sadly sure they would never see their relatives again, but thanks to him they had been reunited.