The third battalion joined the Peninsular Army in 1810. Thereafter the three battalions of the 95th fought in numerous major battles and skirmishes during the Peninsular War as part of the elite Light Division, including the Battle of Bussaco in September 1810 and the sieges of Ciudad Rodrigo in January 1812 and Badajoz and March 1812 as well as the Battle of Vitoria in June 1813. At the Battle of San Marcial in August 1813 a company of the 95th Rifles under the command of Captain Daniel Cadoux held off an entire French division at Vera before withdrawing. The regiment also took part in the Battle of Nivelle in November 1813.