UV excited photoluminescence from BaWO₄ (BWO) single crystals has been investigated in the temperature range of 77–300 K. The presence of two emission bands in the UV and blue spectral regions is observed under excitation by 230nm at room temperature. The observation of UV emission band at room temperature is a novel result. The thermal treatment at elevated temperatures under air or vacuum is observed to influence the optical and luminescence properties of the crystal. The changes brought about by annealing in air are found to be reversible. However, in vacuum annealed samples the UV emission is completely quenched.