The British quiz show which first aired in 1962 pits teams of top University graduates against one another.
The Venerable Paul Ayers, a former student of St. Peter's, Oxford says he was "invited out of the blue" to participate in the special pre-recorded episode due to be broadcast on 30th December.
Archdeacon Paul described the experience as "exciting, scary, stressful and a privilege".
"It's a lot harder than it looks, and it looks really hard," he added.
"It's one thing to try to answer the questions when you're sitting at home; it's another thing with the cameras pointed at you under Jeremy Paxman's gaze."
Fellow team members Gordon Corera (BBC Security Correspondent), Felicity Cloake (Guardian columnist); and human rights lawyer Afua Hirsch will join Archdeacon Paul in representing St Peter's College as they face Trinity Hall, Cambridge.
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