Tuning of vacancies in photocatalytic materials has emerged as a versatile strategy to enhance visible light absorption and photocatalytic activity. In this study, surface oxygen vacancies (defects) were incorporated on antimony tungstate to boost its photocatalytic activity, which was examined by studying the degradation of model pollutants under visible light irradiation. Specifically, a two-to-three-fold increase in photocatalytic activity was observed for oxygen vacancy-rich antimony tungstate in comparison to its pristine counterpart. This improvement in the photocatalytic performance can be attributed to the presence of oxygen vacancies in the material, which leads to an enhanced absorption of light, decrease in the recombination of charge carriers, and increase in the number of active sites. In addition, owing to the nature of the surface charge present, the photocatalysts were found to be selective for the degradation of cationic pollutants in comparison to anionic and neutral pollutants, and can thus be used for the separation of a mixture of pollutants. Furthermore, scavenger studies illustrate that holes play a major role in the photocatalytic degradation of pollutants. Moreover, the excellent photostability of oxygen vacancy-rich antimony tungstate over three consecutive cycles demonstrates its potential as a good photocatalyst for the degradation of pollutants. Overall, this study demonstrates that the engineering of surface vacancies on perovskite oxide materials can render them as efficient single component photocatalysts for environmental remediation applications.