Early logoZambia Airways was founded in 1964 as a subsidiary of Central African Airways. The original fleet consisted of two Douglas DC-3 and three DHC-2 Beaver. By 1967 Zambia Airways had become independent of Central African Airways and acquired a pair of BAC 1-11-207s and a couple of HS.748s. They also leased from Alitalia a DC-8 with which services from Lusaka to London were started. Originally the London route was flown twice a week with intermediate stops at Nairobi, Kenya and Rome, Italy. In 1975 the Boeing 707 replaced the DC-8 and the Boeing 737-200 replaced the BAC 1-11s and was often put into service to Johannesburg and other medium-haul routes.

Another Zambia Airways logoThe widebody era arrived in 1984 with the acquisition of a DC-10. This was the only widebody used by Zambia Airways and was used to open a route to New York, which would at least occasionally make an intermediate stop in Libreville. This first DC-10, registered number 348 and christened "Nkwazi", was reportedly a point of national pride for many Zambian citizens. In 1989, a second DC-10 was leased from Sabena and later Lufthansa to help operate longhaul flights from Lusaka to London, Frankfurt, Rome, and Amsterdam, as well as a weekly service non-stop to Bombay in cooperation with Air India. The author James Ferguson, in his book about Zambian society, also recalls services to Belgrade and Larnaca.

Meanwhile, the ATR 42 replaced the HS.748s. The next fleet expansion consited a of Boeing 757-200F which substituted one of the 707s. Zambia Airways ordered the MD-11 and leased DC-8-61 while waiting for the delivery of the MD-11, which never occurred. In 1992, the government reportedly indicated that the airline would be responsible for its own debt services and had to operating expenses from its own revenues. Under this directive and in a worsening economic climate, the airline very quickly scaled back both domestically and internationally, and was liquidated in 1995.

The carrier Zambian Airways, which in 2007 was the only Zambian airline flying scheduled routes, is unrelated and was derived from the privatised Mines Air Services Limited.