Asencio will head up the team's commercial and marketing operations from New York, starting on 10 April, as the squad looks to grow its financial activities following the takeover by Dorilton Capital in August 2020.
The American's CV includes five years as UFC's senior vice president for global partnerships, where he was responsible for all commercial revenue, as well as almost two years in a similar role at Fanatics.
Asencio rose to prominence at Major League Baseball outfit New York Mets, in a stint spanning 18 years where he ended as senior vice president for corporate partnerships, sales and services.
"As we continue the transformation of Williams Racing, we are delighted to welcome Paul to reinforce our marketing and commercial team," Williams chairman Matthew Savage said in a team statement.
"He has a fantastic track record in global sports including UFC and MLB and we look forward to having him contribute to our journey."
"I'm incredibly excited to be joining Williams Racing. Formula 1 is on a massive growth trajectory and I'm happy to be a part of it," Asencio added.
The appointment comes as the latest new recruit at Williams following Frederic Brousseau being made its new COO and James Vowles joining from Mercedes as its F1 team principal earlier this year.
The shake-up follows the departure of Jost Capito as team boss last December, which was preceded by the exits of Francois-Xavier Demaison as technical director and aerodynamics boss David Wheater.
While the team is still without a permanent new technical chief, design director Dave Worner has stepped into the lead role on an interim basis.
Speaking last month, Vowles confirmed Williams is continuing its search to attract new technical talent and current team members are filling in until a new technical director and head of aerodynamics have been hired.
"Going forward, there's a technical leadership where at the moment, I have lots of people standing in and doing a great job, but we need to supplement them with good experience from industry," Vowles said.
After the Australian GP last weekend, Williams slipped back to the bottom of the F1 world constructors' championship but is level on points with AlphaTauri.
