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Charlie Greene was commissioned a Second Lieutenant and awarded his pilot wings on December 5, 1957. After completing All-Weather Interceptor training, Lieutenant Greene completed F-106 Delta Dart Combat Crew Training and then served with Air Defense Command from August 1958 to May 1961. He left active duty and joined the Air Force Reserve, and then joined the Massachusetts Air National Guard on June 30, 1961, going back on active duty when his unit was activated for the Berlin Crisis on October 1, 1961. Captain Greene deployed with the 101st Tactical Fighter Squadron flying the F-86 Sabre to Phalsbourg AB, France. He then served as Assistant to the Senior Air Force Advisor to the 102nd Tactical Fighter Wing of the Massachusetts ANG, followed by service as an F-105 Thunderchief pilot with the 336th Tactical Fighter Squadron at Seymour Johnson AFB, North Carolina. His next assignment was as an F-105 pilot with the 7th Tactical Fighter Squadron at Spangdahlem AB, West Germany, and then deployed to Southeast Asia with the 333rd Tactical Fighter Squadron at Takhli Royal Thai AFB, Thailand, from December 1966 until he was forced to eject over North Vietnam and was taken as a Prisoner of War on March 11, 1967.

Major Greene was released during “Operation Homecoming” on March 4, 1973. He was briefly hospitalized to recover from his injuries at Westover AFB, Massachusetts, and then received an Air Force Institute of Technology assignment to complete his bachelor's degree at the University of New York. Colonel Greene then served on the staff of Headquarters Tactical Air Command at Langley AFB, Virginia, from May 1976 until his retirement from the Air Force on July 1, 1977.
- Silver Star (2)
- Legion of Merit
- Distinguished Flying Cross
- Bronze Star
- Prisoner of War Medal