Messi tied the knot with his childhood sweetheart, Antonella Roccuzzo, on Friday.
Shakira, 40, wore a chic black dress, which featured a sheer overlay on top of a tulle skirt and completed her look with black stilettos, a gold clutch and her hair styled in a half-up, half-down 'do, reported Entertainment Tonight.
Pique, who also plays for FC Barcelona, sported a classic black tuxedo, bow tie and gigantic grin.
The singer took to Instagram to post a photo of herself and her man in wedding attire with a caption, "Thanks to Antonella and Leo and all the people of Rosario for your hospitality! Shak.