On the outbreak of war in 1793 Pellew was temporarily without a ship, and served as a volunteer aboard his brother's command , being in charge of her aft guns when she captured the on 18 June, the first British naval victory of the French Revolutionary Wars. For this action, his brother was knighted and Israel Pellew was presented to King George III and made post captain of . In April 1795 he was made captain of a larger frigate, , commanding her off Newfoundland and in the North Sea. In September 1796, sailing to join his brother's squadron in the Channel, Pellew took "Amphion" into Plymouth for repairs. On 22 September she suddenly exploded alongside the dock. About 300 of her crew and visitors were killed. Pellew survived, being blown through an open stern gallery window on to the deck of a sheer hulk. An inquiry blamed the explosion on the "Amphion's" gunner, who was suspected of stealing gunpowder which caught fire and blew up the fore magazine. However, Pellew had already complained that the magazine was poorly constructed and unsafe, and questioned the judgement on the deceased gunner.