Colsaerts was part of the European side, captained by Jose Maria Olazabal, in 2012 at Medinah which completed a heroic comeback against the United States.
The Belgian produced a memorable debut when he carded eight birdies and an eagle in partnership with Lee Westwood to help defeat Tiger Woods and Steve Stricker on the final green in the Friday fourball session.
Colsaerts, 40, is a three-time winner on the DP World Tour, most recently at the Open de France in 2019. He entered the week battling to keep his card and he performed in style with a one-shot victory.
He will join Donald's backroom team alongside Dane and 2018 Ryder Cup captain Thomas Bjorn and 2010 Ryder Cup competitor Edoardo Molinari.
"My first reaction when Luke asked me was sheer joy. Every time I hear the words ‘Ryder Cup’, it takes me back to the edition I played in, how proud I was to wear the European colours and be part of such an unbelievable event," Colsaerts said.
"Of course, Luke was in that team too and when we spoke he mentioned how much he has always loved what the Ryder Cup means to me.
"Being a vice captain is a different role to being a player but, nevertheless, my mission in 2023 will be exactly the same as it was in 2012, namely, to make a contribution to the team in any way I can. Rest assured, whatever I am asked to do, I will do it."
Colsaerts will be part of a team that will want to wrestle back the gold trophy which they lost so brutally in 2021. America swept away their opponents 19-9 in Wisconsin, a record-breaking margin.
"Nico has been on my mind for a couple of months now, to be honest. I played in the team with him in 2012 and you could just see how much it meant to him," Donald added.
"He understands what it means to represent the European crest and what it means to be part of the Ryder Cup set-up. When I asked him, he literally had goosebumps - so I am very happy to have him as my third vice captain."
"Nico gets along extremely well with all the guys out here on the DP World Tour and he will be a great person to help keep an eye on things here in Europe in periods when I might be in the US.
"There is already great communication between us - myself, Thomas, Edoardo and Nico - and I couldn’t be happier with the way my backroom team is shaping up."