Jolliffe was educated at Hastings Grammar School before studying French at University College London. Jolliffe married Beryl Bailey, with whom he would go on to have three daughters. He was appointed Assistant Keeper in the Department of Printed Books at the British Museum in 1955, moving to Oxford to become Keeper of Catalogues at the Bodleian Library in 1970. He was a fellow of Nuffield College, Oxford from 1971 onwards. He became Bodley's Librarian in 1982 at a time of budget cuts, having earlier been Acting Librarian.
