The BBC reported Sunday the show's producers were on the brink of inviting the head of the Church of England on to the animated show.
Williams has admitted he is a big fan of the show.
"We'd look at it very seriously; it would be a very interesting thing to do," his spokesman said.
Williams has said in the past that the show was "on the side of the angels."
The Simpsons producer Al Jean reportedly said they had been flattered by Williams' support and, "We'd love to have him on the show."
The archbishop's spokesman said Sunday no invitation had yet been made, but Williams "had said a lot of positive things about the show, and it has a lot of merit."