Neville sat in Parliament as the member for New Windsor (1584, 1586 and 1593), Sussex (1589), Liskeard (1597) and Berkshire (1604, 1614). He served as High Sheriff of Berkshire in 1595. Before his father's death, he lived at the old Archbishop's Palace at Mayfield in Sussex, inherited from his great-uncle Sir Thomas Gresham (died 1579), where he ran a highly successful cannon manufactury. He was appointed Deputy Lieutenant of Berkshire in 1596 and moved to Billingbear the next year. He was knighted in 1599.