Bismuth vanadate (BiVO4) has been widely used as a photocatalytic semiconductor for oxygen evolution in artificial photosynthesis. In this study, one-dimensional mesoporous BiVO4 nanofibers (BiVO4 NFs) were fabricated by the electrospinning strategy. The NFs were then deposited with NiCo layered double hydroxides (NiCo LDHs) to improve their reaction kinetics, charge transfers, and water oxidation activities. The obtained BiVO4/4 wt%NiCo LDHs composite exhibits enhanced photocatalytic oxygen oxidation activity that is approximately 1.6 times higher than that of BiVO4 NFs, due to the synergistic effects between BiVO4 NFs and NiCo LDHs, which can accelerate the transfer of holes between their surfaces. This design is a promising approach for fabricating large-scale nanofibers with good photocatalytic performance.