The pair – who have been married for eight years – laughed out loud with the movie's director and co-writer George Clooney as they posed for photographs at international event at the Berlin Film Festival.
Matt looked dapper in a grey suit and black shirt, and Luciana looked particularly stunning in a white dress with a sparkle embellishment as well as red and gold peep-toe heels.
Matt and George were joined by fellow co-stars Bob Balaban and Justus von Dohnányi, as well as John Goodman, who wrapped up warm in a charcoal grey coat over his suit.
The 61-year-old star seemed to be enjoying taking the event in as he took some pictures on his mobile phone while on the red carpet at the Berlinale Palast venue.
Hugh Bonneville and his wife Lulu Williams also walked the red carpet at the film festival looking smart, and German actress Sinta Weisz added some extra glamour to the red carpet in a green dress.
George and co-star Dimitri Leonidas posed with real-life Monuments Man Harry Ettlinger, who volunteered his services when he was a 19-year-old American soldier after learning the Monuments Men needed someone who spoke German.
John was all smiles at the premiere and also dressed up for the occasion in a grey coat and red tie.
But Cate Blanchett, who plays Claire Simone in the movie, wasn't able to attend the premiere as she was in New York on Friday to mourn the death of late actor Phillip Seymour Hoffman.
