The Irishman will lead from the front at the first tee alongside the 2012 Qualifying School winner John Parry and 2012 Challenge Tour Number One Espen Kofstad.
“I am absolutely thrilled to be striking the first shot in the race for The 2014 Ryder Cup,” said McGinley. “While I have obviously ruled myself out of the running to battle for a place in the team, as the Captain and the leader I am extremely proud to lead the lines for my prospective team members.
“There is going to be fierce competition for those nine spots and I'm sure there are many players at The Celtic Manor Resort this week with their eyes focussed firmly on a place in my team.
“It also gives me great pleasure to hit the first shot of the tournament, as this is always been a special event for me, especially since my victory here at The Celtic Manor Resort in 2001.”
McGinley will be joined by two players who know all about making the grade in high-pressured qualification processes, with Parry having won Qualifying School in December of last year to claim the first card for The 2013 Race to Dubai.
Kofstad, meanwhile, produced a magnificent performance on the final day of the 2012 Challenge Tour Grand Final to claim the title and in the process seal a rookie season on The European Tour.
Thongchai Jaidee will begin the defence of his title at 13:15 playing alongside 2011 Open Champion Darren Clarke and Spain’s Rafa Cabrera-Bello.
Other groups which catch the eye include the 08:05 group of Spaniards Miguel Angel Jiménez and Gonzalo Fernandez-Castaño and Denmark’s Thorbjørn Olesen, who start on the 11th tee.
Last week’s winner on The European Tour at the Johnnie Walker Championship at Gleneagles, Tommy Fleetwood, plays in the group immediately afterwards - on the 11th tee at 08:15 - alongside 2010 Ryder Cup European team member Francesco Molinari and Finland’s Mikko Ilonen.
One of the home hopes and the course record-holder at The Celtic Manor Resort, Rhys Davies, will play alongside American Peter Uihlein and Frenchman Raphaël Jacquelin.