After graduating last in his class from the U.S. Military Academy at West Point, N.Y., (1846), Pickett served with distinction in the Mexican War (1846–47). He resigned his commission in June 1861 and entered the Confederate Army, in which he was made brigadier general in February 1862. Pickett rose to major general in October and was given command of a Virginia division. At the Battle of Fredericksburg he commanded the centre of Gen. Robert E. Lee's line but saw little action.

At Gettysburg (July 3, 1863) three brigades of Pickett's division (4,300 men) constituted somewhat less than half the force in the climactic attack known as Pickett's Charge. The attack was actually under the command of Gen. James Longstreet (Longstreet, James). Its bloodily disastrous repulse is often considered the turning point of the war. Although Pickett was much criticized and charged by some with cowardice, Lee retained him in divisional command throughout the Virginia Campaign of 1864. Eight days before the surrender at Appomattox (April 9, 1865), Pickett's division was almost destroyed at Five Forks while he was attending a shad bake. After the war he worked in an insurance business in Norfolk, Va.