The present work reports the photocatalytic properties of pyrolyzed molybdenum oxide thin film. Microstructural analysis reveals clustered nanoaggregates. Structural analysis shows polycrystalline 𝛼-MoO3 phase. The crystallite size, dislocation density, microstrain and stacking faults are found to be 41.27 nm, 5.87 ×10−4 lines/cm2, 8.41 ×10−4 and 1.78, respectively. The optical bandgap is found to be 3.20 eV. Linear sweep voltammetry measurement in 1 M KOH electrolyte reveal significant photocurrent density of 992.39 𝜇A/cm2 at bias of 1 V vs. Ag/AgCl. The reasonable performance of the device suggest that the spray pyrolysis method is promising for preparing photosensitive MoO3 films for photoelectrochemical measurement.