The Ti3+ self-doping B-TiO2/g-C3N4 hollow core-shell nano-heterojunction is synthesized via the continuous hydrothermal deposition and sculpture-reduction processes. The results of SEM, XRD, TEM, XPS and FT-IR imply that the B-TiO2/g-C3N4 hollow core-shell nanospheres have been prepared successfully. The photocatalytic activity of the B-TiO2/g-C3N4 nano-heterojunctions remarkably exhibits an enhancement of 18 times and 65 times than that of normal TiO2 and g-C3N4, respectively. Further, the photocatalytic process and the mechanism of the photocatalytic hydrogen production enhancement have been studied, which could be ascribed to the O-v-Ti3+ in the B-TiO2 and interface nano-heterojunction, that have been proved by the transient photocurrent, PL, EIS and Mott-Schottky plots.