This work investigates a series of BiVO4 with different (010) and (110) facets ratio. The crystal structure, morphology, and photophysical properties of BiVO4 samples were all characterized by XRD, FE-SEM, TEM, XPS, PL, UV–vis and BET techniques. Photocatalytic performances of BiVO4 samples with different (010) and (110) facets ratio were evaluated by the O2 evolution and decolorization of thymolblue under the simulated sunlight irradiation. It showed that a positive relationship exists between the photocatalytic activities (O2 evolution) and the (010) facet ratio. The plate-like msBiVO4 exhibited exceptional O2 evolution ability approximately 4 times greater than bipyramid msBiVO4 under the simulated sunlight. The photocatalytic performances of plate-like msBiVO4 mainly originates from the weak-binding effect of (010) facet for photo-generated carrier compared with (110)-dominant msBiVO4. The built-in of inner electric fields directed from (110) facet to (010) facet, further enhancing the transfers of photo-generated electron–hole pairs by the action of potential energy difference. The entirely exposed (110) facet of msBiVO4 in this study provides us with an opportunity to explore the key factor for its photocatalysis. •The (110)-dominant and (010)-dominant msBiVO4 samples have been successfully synthesized.•The space charge layer width has positive correlation with the percentage of (010)/((110)+(010)) for msBiVO4.•The electric potential difference between (010) and (110) of msBiVO4 is important for efficient carrier separation.