Rare-earth aluminate garnet-type double oxides have practical applications as scintillators with high luminescence yields; however, several garnet compounds are metastable phases, and those scintillation properties are yet unclear. We prepared Ce3+-doped Gd3Al5O12 (Ce3+:GAG) as a thick-film phosphor, using laser-assisted metal–organic chemical vapor deposition, and investigated its luminescence and scintillation properties. With a deposition rate of 48 μm h−1, the Ce3+:GAG thick film was epitaxially grown on a Y3Al5O12 single crystal substrate with in-plane orientation relationship. Under UV light and α-ray irradiations, the Ce3+:GAG film exhibited a broad emission centered at 560 nm corresponding to the 5d–4f transition of Ce3+ ions. The scintillation light yield of the Ce3+:GAG film was 14250 photons per 5.5 MeV with a fast decay constant of 82.8 ns for the α-ray irradiation from the 241Am source.