White was born on November 14, 1930, in San Antonio, Texas, to parents Edward H. White, Sr. (1901–1978), who became a major general in the U.S. Air Force, and Mary Rosina White (née Haller; 1900–1983). He attended school in his hometown and became a member of the Boy Scouts of America, where he earned the rank of Second Class Scout. After graduation from high school in 1948, he was accepted to the U.S. Military Academy at West Point, where in 1952 he earned his Bachelor of Science degree and was commissioned as a Second Lieutenant in the Air Force. White then chose a commission with the U.S. Air Force and attended flight school, a course that takes just over a year. Following graduation from flight school, White was assigned to the 22nd Fighter Day Squadron at Bitburg Air Base, West Germany. He spent three and a half years in West Germany flying in F-86 Sabre and F-100 Super Sabre squadrons in the defense of NATO.  After graduating from West Point, Ed competed for s spot on the U.S. Olympic team in the 400 meter hurdles race. He missed making the team by only 1/10 second. His hobbies included squash, handball, swimming, golf, and photography.

In 1958, White enrolled in the University of Michigan under Air Force sponsorship to study Aeronautical Engineering, where he earned his Master of Science degree in 1959. Following graduation, White was selected to attend the U.S. Air Force Test Pilot School at Edwards Air Force Base and was then assigned as a test pilot at the Aeronautical Systems Division at Wright-Patterson Air Force Base. During his career, White would log more than 3,000 flight hours with the Air Force, including about 2,200 hours in jets, and would ultimately attain the rank of Lieutenant colonel.  In 1953, White married Patricia Finegan, whom he met while at West Point. The Whites would have two children, Edward White III (born 16 September 1953) and Bonnie Lynn White (born 15 May 1956). White was a devout Methodist.

White was one of nine men chosen as part of the second group of astronauts in 1962. Within an already elite group, White was considered to be a high-flier by the management of NASA. He was chosen as Pilot of Gemini 4, with Command Pilot James McDivitt. White became the first American to make a walk in space, on June 3, 1965. He found the experience so exhilarating that he was reluctant to terminate the EVA at the allotted time, and had to be ordered back into the spacecraft. While he was outside, a spare thermal glove floated away through the open hatch of the spacecraft, becoming an early piece of space debris in low-earth orbit, until it burned up upon re-entry into the Earth’s atmosphere. There was a mechanical problem with the hatch mechanism, which made it difficult to open and to relatch, which added to the time constraint of the spacewalk, and could have threatened the lives of both men if McDivitt had been unable to get the hatch latched, as they could not re-enter the atmosphere with an unsealed hatch.  White’s next assignment after Gemini 4 was as the back-up for Gemini 7 Command Pilot Frank Borman. He was also named the astronaut specialist for the flight control systems of the Apollo Command/Service Module. By the usual procedure of crew rotation in the Gemini program, White would have been in line for a second flight as the Command Pilot of Gemini 10 in July 1966, which would have made him the first of his group to fly twice.

In March 1966 he was selected as Senior Pilot (second seat) for the first manned Apollo flight, designated AS-204, along with Command Pilot Virgil “Gus” Grissom, who had flown in space on the Mercury 4 Liberty Bell 7 mission and as commander of the Gemini 3 Molly Brown mission, and Pilot Roger Chaffee, who had yet to fly into space. The mission, which the men named Apollo 1 in June, was originally planned for late 1966 (perhaps concurrent with the last Gemini mission), but delays in the spacecraft development pushed the launch into 1967.  Launch of Apollo 1 was planned for February 21, 1967, when the crew entered the spacecraft on January 27, mounted atop its Saturn IB booster on Launch Pad 34 at Cape Kennedy, for a “plugs-out” test of the spacecraft, which included a rehearsal of the launch countdown procedure. Mid-way through the test, a fire broke out in the pure oxygen-filled cabin, killing all three men.

White’s job was to open the hatch cover in an emergency, which he apparently tried to do; his body was found in his center seat, with his arms reaching over his head toward the hatch. Removing the cover to open the hatch was impossible, because the plug door design required venting normally slightly greater-than-atmospheric pressure and pulling the cover into the cabin. Grissom was unable to reach the cabin vent control to his left, where the fire’s source was located. The intense heat raised the cabin pressure even more, to the point where the cabin walls ruptured. The astronauts were killed by asphyxiation and smoke inhalation.  The fire’s ignition source was never determined, but their deaths were attributed to a wide range of lethal hazards in the early Apollo Command Module design and workmanship, and conditions of the test, including: the highly pressurized 100% oxygen pre-launch atmosphere; many wiring and plumbing flaws; flammable materials used in the cockpit and the astronauts’ flight suits; and the hatch which could not be opened quickly in an emergency. After the incident, these problems were fixed, and the Apollo program carried on successfully to reach its objective of landing men on the Moon.

White was buried with full military honors at West Point Cemetery while Grissom and Chaffee are both buried in Section 3 (GPS Coordinates: 38.873115 N, -77.072755 W) of Arlington National Cemetery.  In 1997, White was posthumously awarded the Congressional Space Medal of Honor. White was inducted into the U.S. Astronaut Hall of Fame in 1993 and the National Aviation Hall of Fame on July 18, 2009.  White’s wife Patricia remarried and continued to reside in Houston. On September 7, 1983 she committed suicide after surgery earlier in the year to remove a tumor.