Murino was born in Cagliari, Sardinia, and initially wanted to be a doctor. She finished fourth in the 1996 Miss Italy contest. Having moved to London, she fell in love with theatre and acting, saving up weekly to watch something in the West End theatre.
Returning to Italy, she studied drama at the Scuola di Cinema e Teatro run by Francesca De Sapio, between 1999 and 2000. She then appeared in stage productions of Richard III and Italian language plays. She began her career in television in 2002, and then gained international fame after playing Solange Dimitrios in the 2006 adaptation of the James Bond novel Casino Royale.
In early 2011, she co-starred with Rufus Sewell in the BBC One TV series Zen. Zen has since been cancelled, although it is airing in the U.S. on Masterpiece Mystery.
In 2011 she also appeared in Bob Sinclar's music video clip Far l'amore. She is also starring the video clip of the famous party band The Gypsy Queens "l'Italiano", produced by Didier Casnati
In 2013, she starred as Penelope, Ulysses' wife for a TV production Odysseus.
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