Two-dimensional (2D) heterostructures of black phosphorus (BP)/bismuth vanadate (BVO) have attracted much attention due to their potential uses in photocatalytic water splitting. However, the interfacial photoinduced electron- and holetransfer dynamics are not explored computationally. Herein, we have used density functional theory (DFT) calculations and DFT-based fewest-switches surface-hopping dynamics simulations to investigate the light-driven electron and hole dynamics taking place at the interface of BP and the BVO(010) surface. Our results show that the BP monolayer is adsorbed on BVO(010) via van der Waals interaction. Upon irradiation, the electron transfer takes place from BP to BVO(010) within 500 fs but with two distinct processes. In the first phase, the electron transfer proceeds adiabatically and is mainly driven by atomic motions. In the second phase, the electron transfer decays very slowly. The hole-transfer dynamics from BVO(010) to BP exhibits a similar ultrafast decay in the first stage followed by a slow decay; however, there is a comparable amount of hole trapped in a BP state due to a large energy gap from its higher state. These insights may be useful for the design of novel photocatalytic water-splitting materials.