The cleaning of water contaminated with organic dyes is a crucial problem nowadays. The search for good catalysts is intense, and bismuth tungstates have attracted a lot of attention because of their catalytic properties which are related to their crystal structure and morphology. In this study, we show that Bi2WO6 (BWO) crystals synthesized by the surfactant-assisted hydrothermal method create a different morphology than non-assisted crystals. With the assistance of the PVP surfactant, even the BWO crystalline structure could change, crystallizing into a high-symmetry metastable phase. These changes in morphology imply a decrease in BWO catalytic activity, which shows that insightful control of BWO synthesis is necessary to improve the BWO properties.