Motorsport.com revealed ahead of the season-opening Bahrain Grand Prix that Mercedes had hired former Red Bull COO and HR director Poole as a new special advisor.
Her role was to evaluate the strengths and weaknesses of the current infrastructure at Mercedes and offer advice on where improvements could be made.
As the German manufacturer continues its efforts to return to the front in F1, Wolff has praised the input that Poole has made, which has included "forensic profiles" of the best targets in the paddock.
"Jayne is a person that I admired over the last 10 years, that I got to know 10 years ago, and I always had a very respectful relationship with," said Wolff in an exclusive interview reflecting on the Mercedes team.
"She worked for the competitor, but you can respect people working for a competitor and acknowledge their performance. Her role at Red Bull was, in my opinion, a very large part of the success of the team over the last years.
"That relationship came to an end, like many relationships come to a natural end. I wanted to hire Jayne for a long time, but it was just never an option. And then it became now.
"She's a great addition. She has a lot of know-how, she's a great psychologist, she has seen another organisation, she knows everybody pretty much, and she has created forensic profiles of all of the good people in Formula 1. Having her eyes is a very, very strong edge to the organisation."
While Wolff helped guide Mercedes to eight consecutive F1 world title doubles, he said getting outsiders, like Poole, into the team was essential to help it adapt and thrive.
"Now and then, if an organisation becomes mature and follows its processes and strategies, and it's successful, you need to get an outside perspective, and you need to shake it up," said Wolff about making use of those who know how other teams work.
"You don't want to reinvent it, but you want to consider whether yesterday's assumptions are still competitive enough going forward. And therefore, having somebody come in with fresh eyes, looking at it in a very neutral way, is beneficial.
"So, from time to time, even in a successful organisation, you need to parachute good external people in, because they help you to do the next step."