The Swede, who has played five times in the biennial contest, joins compatriot Robert Karlsson, Englishman Luke Donald, Germany’s Martin Kaymer and Graeme McDowell of Northern Ireland in the role.
Between them, the quintet boasts the experience of 19 Ryder Cups for Europe and 40 points scored.
It will be Stenson’s first stint as vice captain, having produced a bold late bid to get himself into the mix for a captain’s pick only to come up short in the end.
Stenson said: “It’s a great honour to get the call and to be involved with Team Europe.
“I’ve been part of five Ryder Cup teams in the past and to be given the opportunity as a vice captain to help Europe’s quest to retain the Ryder Cup is exciting.
“Pádraig called me on Monday morning and it was not a long conversation. I accepted straight away and I assured him that myself, along with the other vice captains, are there to help and assist him and the team in any way we can.
“We have a very strong team. It’s a mix of huge experience along with three guys who will take on their first Ryder Cup – and that’s a great combination. We have strength in depth so I’m looking forward to getting out there and seeing the boys perform."
While it is not known if Justin Rose was considered for the post after missing out on a wildcard, Harrington is “delighted” to have Stenson in his backroom team.
The European captain said: “Following on from Sunday when the 12 players were confirmed, we now have Team Europe complete and I could not be happier.
“Henrik will bring so much to the week in all aspects both on and off the course. His playing record speaks for itself and he has the full respect and confidence of all the players.
“He knows what it takes to win a Ryder Cup and that experience and knowledge will be crucial for us. Henrik’s renowned wit and sense of fun will also benefit our team room immensely.”