In the present study, BiVO₄ sample was prepared under different pH 0.5–13 without capping agent. Different morphology characteristics were observed, such as sheet crystal structure, cross crystal structure and branching crystal structure. The mechanism of the formation of BiVO₄ nanostructure was discussed. Under acid condition, sheet crystal structure was obtained. The phenomenon could be attributed to polymerization of vanadate in the presence of H⁺. In the weak alkaline solution, across structure and branching type morphology was obtained. The photocatalytic efficiency for the samples ranked as pH 5 > pH 3 > pH 7 > pH 9 > pH 1 > pH 11 > pH 13 > blank, which is in good agreement with X-ray diffraction (XRD) result. E. coli envelop was damaged in the presence of BiVO₄ under visible light. The protrusion on envelop was diminished by BiVO₄. Attenuated Total Reflection Fourier transformed Infrared Spectroscopy (ATR-FTIR) results suggested the intensity was weakened for the amide, phosphoric, –COO⁻ group and C-H bond in lipopolysaccharides (LPS), peptidoglycan and periplasm molecules.