The morphology of the primary semiconductor material is an essential factor for the performance of photocatalysts. In this work, we synthesized the cubic facet (100) and the anisotropic facets ((100) and (110)) of NaTaO3 as photocatalysts. They were assessed by the photocatalytic conversion of CO2 using H2O as the electron donor and a series of cocatalysts, including Ga(OH)3, Cd(OH)2, Zn(OH)2, and amorphous ZnGa2O4, relative to Ag nanoparticles as a conventional cocatalyst. The results demonstrated that anisotropic NaTaO3 favored higher formation rates of CO than the cocatalysts, including Ga(OH)3, Zn(OH)2, amorphous ZnGa2O4, and Ag nanoparticles, while the Cd(OH)2 cocatalyst exhibited higher performance than cubic NaTaO3.