Bjorn is no stranger to Ryder Cup success, having captained Europe to victory at Le Gold National in Paris back in 2018. The Dane has featured in three of the biennial contests and was a vice-captain on four previous occasions.
Speaking about the selection, Stenson said: "I have known Thomas for my whole career. I trust him implicitly and I know any advice he will give me will be honest and direct.
"He will not simply tell me what he thinks I want to hear and that will be important, so I'm delighted to have him as my first vice-captain for Rome.
"Since the match itself is still over a year away, I know I am going to have a lot of conversations with him about all elements of the Ryder Cup from his experience, both as a vice-captain on previous occasions but also, obviously, as the captain in 2018 when we had a great result.
"I will be depending on him a lot and I'm really looking forward to those chats.
"He was very happy when I asked him. He was very honoured to be asked and happy to be part of Team Europe again and part of the journey with the players."
Stenson was one of Bjorn's 12 players during their successful Ryder Cup bid back in 2018.
Speaking about his appointment as vice-captain for the 2023 event, Bjorn added: "I'm delighted to be part of the whole Ryder Cup experience once again.
"I probably thought that after 2018 that was it for me, but Henrik called me to talk about captaincy in general and that led into him asking me if I wanted to do another stint as vice-captain, which I agreed to. I'm excited to work with him.
"I think I can help Henrik outline what he wants to do with his captaincy going forwards. I can keep asking him the right questions and reminding him of things that are going to come his way that he might not have thought about.
"I will help him prepare in the best possible way and, as we get closer to the match, to be an additional support to the players.
"I think Henrik will be a fantastic captain. He is so well respected by players and by everyone in the game. He is a very hard-working golfer and somebody who is true to himself, and his team will represent that.
"He has a great sense of humour that the players will take to, and he is very well liked across the whole Tour, not just the top where he has played his golf for so many years."
Europe will attempt to regain the trophy when the event, held in Italy's Marco Simone Golf and Country Club, gets underway on September 29, 2023.
The United States won the 2021 Ryder Cup 19-9 at Whistling Straits - just their third victory since the turn of the century.