A series of Ce 3+ doped ␣-Sr 2−2x Ce x Na x P 2 O 7 phosphor compounds has been prepared using a high-temperature solid-state reaction technique. The luminescence properties under vacuum ultraviolet-UV and x-ray excitation were studied. Luminescence spectra reveal three UV-emitting peaks at about 310, 330, and 350 nm from which we conclude that Ce 3+ occupies two distinct sites in ␣-Sr 2 P 2 O 7 . The influences of the doping concentration, the temperature, and the excitation wavelength on the luminescence of Ce 3+ at the Ce͑I͒ and Ce͑II͒ sites together with the decay characteristics are discussed. The light yield under x-ray excitation is found to be around 10 000 photons/MeV.