A surfactant-free solvothermal method was developed for the controlled synthesis of diverse 3D ms-BiVO4 superstructures, including a flower, a double-layer half-open flower and a hollow tube with square cross-sections, via facilely adjusting the pH values with the aid of NH3·H2O. The effects of the morphologies of the prepared 3D ms-BiVO4 superstructure on the photocatalytic oxidation of NO were investigated, indicating that the enhanced photoactivity was not related to the surface area, but associated with the unique morphology, surface structure and good crystallinity. Moreover, the flower-like ms-BiVO4 photocatalyst with a more (040) reactive crystal plane exhibited higher photoactivity than those of other samples. The unique morphology helped with flushing the oxidation products accumulated on the surface of photocatalysts in the H2O2 system, and further improved the photoactivity. A trapping experiment was also conducted to examine the effects of the active species involved in the PCO of NO intuitively.