The foursomes match between Europe's Jon Rahm and Tyrrell Hatton and USA's Scottie Scheffler and Sam Burns will kick off the 44th Ryder Cup on Friday.
At the end of the opening ceremony at the Marco Simone Golf and Country Club, there was much anticipation over who would be selected by Luke Donald and Zach Johnson respectively.
While Rahm and Hatton were a fancied pairing for the home side, world number one Scheffler was paired with Ryder Cup rookie Burns.
Viktor Hovland - who hit a hole-in-one at a Par 4 earlier on Thursday - will partner Scandinavian compatriot Ludvig Aberg - another rookie - in the second contest against competition newcomers Max Homa and Brian Harman.
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Another Ryder Cup rookie in Sepp Straka will feature for Europe in the third match, with the Austrian partnering Shane Lowry versus the American pairing of Rickie Fowler and Collin Morikawa.
The final encounter sees Rory McIlroy and Tommy Fleetwood team up against Xander Schauffele and Patrick Cantlay.
Friday's foursomes
6.35am (BST): Jon Rahm/Tyrrell Hatton vs. Scottie Scheffler/Sam Burns
6.50am (BST): Viktor Hovland/Ludvig Aberg vs. Max Homa/Brian Harman
7.05am (BST): Shane Lowry/Sepp Straka vs. Rickie Fowler/Collin Morikawa
7.20am (BST): Rory McIlroy/Tommy Fleetwood/ vs. Xander Schauffele/Patrick Cantlay