Coupling oxidation type semiconductors is a feasible strategy to improve the photocatalytic activity of reduction type g-C3N4 photocatalysts. In this work, Bi2O3 was used as an oxidation type semiconductor to construct direct Z-scheme Bi2O3/g-C3N4 photocatalysts by a one-step calcination method. The obtained Bi2O3/g-C3N4 composites exhibited excellent photocatalytic activity and stability toward methylene blue degradation under visible light irradiation. The composite with 1% weight content of Bi2O3 to g-C3N4 exhibited the highest photocatalytic activity with an apparent rate constant of 0.063 min−1, which was 3.0 and 3.7 times higher than that of pure Bi2O3 and g-C3N4, respectively. The enhanced photocatalytic activity of the Bi2O3/g-C3N4 composite was mainly attributed to the improved charge separation efficiency and stronger redox ability. This work gave a new insight in developing g-C3N4-based Z-scheme heterojunction photocatalysts with enhanced photocatalytic activity.