Wollaston was elected a Fellow of the Royal Society in 1786. From 1792 to 1813 he was Jacksonian Professor at Cambridge. Resigning his Trinity Hall fellowship to marry Frances Hayles in 1793, he became Rector of South Weald the following year. In 1807 he was elected Master of Sidney Sussex College, but the election was declared invalid on the grounds that he had never been a fellow of Sidney Sussex. On resigning his professorship in 1813, he assumed additional clerical duties: from 1813 to 1823 he was rector of Cold Norton and archdeacon of Essex.