Photocatalysis is a green technique that can convert solar energy to chemical energy, especially in H₂ production from water splitting. In this study, ZnO and red phosphorus (ZnO/RP) heterostructures were fabricated through a facile calcination method for the first time, which showed the considerable photocatalytic activity of H₂ evolution. The photocatalytic activities of heterostructures with different ratios of RP have been investigated in detail. Compared to bare ZnO, ZnO/RP heterostructures exhibit a 20.8-fold enhancement for H₂ production and furthermore overcome the photocorrosion issue of ZnO. The improved photocatalytic activities highly depend on the synergistic effect of the high migration efficiency of photo-induced electron–hole pairs with the inhibited charge carrier recombination on the surface. The presented strategy can also be applied to other semiconductors for various optoelectronics applications.