There have been several regiments in the British Army numbered as the 95th Regiment of Foot. Perhaps the most famous was formed in 1800 as an "experimental Corps of Riflemen" who armed with the Baker rifle, would act as skirmishers against the French during the Napoleonic Wars. This unit was later renamed in 1816 as The Rifle Brigade, with its number taken by the 96th Foot, which was disbanded in 1818.

The purpose of the regiment was to have the riflemen working in open order and be able to think by themselves, a method completely unheard of prior to its formation. They were to operate in pairs and make best use of natural cover from which to harass the enemy with accurately aimed shots as opposed to releasing a mass volley, which was the orthodox of the day. On top of this the units operation was markedly different to the line infantry by being taught instead of flogged, holding regular shooting and sporting competitions and by being rewarded for achievements. Officers would regularly dine with their men and in so doing would become familiar with each man in their respective companies, again a discipline unheard of at the time.

The performance of the regiment can be demonstrated by the story of Rifleman Thomas Plunkett of the 1st Battalion, 95th Rifles. Who armed with a Baker rifle,shot General Colbert at a range of between 400 and 600 yards during the Peninsula War. He then shot a second Frenchman who rode to the general's aid, so proving that it was not just a lucky shot. By comparison a standard issue Brown Bess musket could not be relied upon to hit a man-sized target at over 60 yards.

A rifleman was dressed in distinctive dark green uniforms, as opposed to the bright red coats of the British Line Infantry regiments. This tradition can be seen in the regiment’s modern equivalent, The Royal Green Jackets.

The regiment fought in all campaigns during the Napoleonic Wars, seeing sea-service at the Battle of Copenhagen, were engaged in most major battles during the Peninsular War in Spain, forming the rearguard for the British armies retreat to Corunna, were sent as an expeditionary force to America in the War of 1812 and, held their positions against tremendous odds at the Battle of Waterloo.