After World War II, Walker spent 21 years working as a test pilot. In 1960, he made the first test flight of the X-15 aircraft; Walker would go on to fly the X-15 24 times, including the only two flights of the X-15 to exceed 100 kilometers in altitude, Flight 90 (19 July1963; 106 km) and Flight 91 (22 August1963; 108 km).
One of the first Fellows of the Society of Experimental Test Pilots, Walker was killed on June 8, 1966, in a collision between his F-104 chase plane and an XB-70. Walker was married and had four children.