The fusiform g-C3N4/CaTiO3 nano-heterojunctions is synthesized via simple preparation using the hydrothermal co-deposition method. The results of morphology and structure imply that the g-C3N4 has deposited on the surface of fusiform CaTiO3 successfully, and the photocatalytic activity of the g-C3N4/CaTiO3 nano-heterojunctions exhibits a remarkably enhancement of 18 times than that of the unmodified sample. Further, proved by the transient photocurrent, PL, EIS and Motty-Scotty plots, the photocatalytic hydrogen production enhancement could be ascribed to the nano-heterojunction at the interface. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.