The Red Kites received a number of applications, but the former Aylesbury United boss was the stand-out candidate based on his track record and his vision for the club
Williams managed Aylesbury from 2017, first as caretaker manager and then on a permanent basis until October 2022.
He guided the team to safety and was in charge for 177 games, making him the Ducks` third-longest serving manager.
His track record of developing numerous players who have gone on to play at higher levels speaks to his ability.
Thame chairmen Richard Carr said: "We are extremely happy to welcome Ben to Thame. His knowledge of local players combined with belief in giving youth a chance makes him the perfect fit."
Williams said: "I am excited to be joining Thame United. The club have sold me a great project to me and something I feel I can help with. I have been made to feel very welcome already and I'm looking forward to meeting everyone and getting started next week".
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