He joined the staff of the Apostolic Signatura in 1972. On 21 December 1982 he was appointed titular bishop of Acropolis, and he received his episcopal consecration on the following 6 January from Pope John Paul II, with Archbishops Eduardo Martínez Somalo and Duraisamy Lourdusamy serving as co-consecrators. John Paul promoted Grocholewski to the rank of Archbishop on 16 December 1991. On 15 November 1999, John Paul appointed him Prefect of the Congregation for Catholic Education. That position made him "ex officio" Grand Chancellor of the Pontifical Gregorian University.