Transparent GdTaO4:Eu3+ thick films were prepared from the inorganic salt and 2-methoxyethanol solution containing polyvinylpyrrolidone (PVP) via sol–gel technique. The critical thickness of the film, i.e. the maximum thickness achievable without crack formation via non-repetitive deposition, was 0.8 μm. The effect of PVP on the morphology, crystallization behavior and optical property of the GdTaO4:Eu3+ thick film was investigated. The results indicated that PVP could play an important role in the formation of transparent GdTaO4:Eu3+ thick films, suppressing the stress evolution, adjusting the sol viscosity, ameliorating the crystallinity, and strengthening the covalency of Eu–O bonds. The GdTaO4:Eu3+ thick films prepared with PVP exhibited a superior photoluminescence and X-ray exited luminescence, which implies that it will have promising applications in high-spatial-resolution X-ray imaging and flat panel display devices.