The New York designer was apparently surprised to see the singer – who he worked with on her Louis Vuitton Autumn/Winter campaign - and her boyfriend. The couple made a last minute decision to attend after Jesus had walked the catwalk for Adidas line Y-3.
There was also a chance for Madonna to catch up with flamboyant pop siren Lady GaGa at the event.
The platinum-haired singer, typically quirky in a Venetian ball-style eye mask, asymmetrical hat and an oversize white blazer, has clearly made an impression on Madonna.
After the pair chatted at the MTV awards on Sunday night, the queen of pop told press: "I just saw Lady GaGa. She looks like she’s going to carnival in Venice, very beautiful."
And when asked if she was bothered by comparisons between herself and the Poker Face singer, Madonna replied: "No, I'm very flattered."
Both were on hand to check out Marc's new collection. Underwear as outerwear was one of the key looks - fitting for Madonna, who championed the conical bra in 1993.
There was also a mix of the understated - in the form of a simple cotton shirt, a belted grey trench coat and a pair of blue tapered trousers - and the less modest.
Most of the over garments came with frills running up their sleeves or cascading down their backs and fabrics were opulently expensive. Harem pants came in a violet jacquard, while jackets were in multi-coloured metallic silk.