Due to the aggravation of environmental pollution and the energy crisis, it is urgent to develop and design environment-friendly and efficient photocatalysts for water splitting. van der Waals heterostructures composed of different two-dimensional materials offer an easily accessible way to combine properties of individual materials for applications. Herein, a novel Cs3Bi2I9/C2N heterostructure is proposed through first-principles calculations. The structural, electronic, and optical properties, as well as the charge transfer mechanism at the interface of Cs3Bi2I9/C2N are systematically investigated. Due to the difference between the work functions of Cs3Bi2I9 and C2N monolayers, when they are constructed into heterostructures, redistribution of charge occurs in the whole structure, and some of the charge transfer occurs at the interface due to the formation of an internal electric field. The band structure of Cs3Bi2I9/C2N has type-II band alignment, and the band edge position as well as the band-gap value of the heterostructure are suitable for visible light water splitting. The in-plane biaxial strain, interfacial spacing, and external electric field can effectively modulate the electronic structure and photocatalytic performance of the heterostructure. Under certain conditions, the heterostructure can be changed from type-II to type-I band alignment, accompanied by the transition from an indirect band-gap semiconductor to a direct band-gap semiconductor. Moreover, the intrinsic anion defect (I vacancy) at different positions, as donor defects, can introduce defect levels near the conduction band edge, which affects the transition of photogenerated carriers in these systems. Our findings provide a theoretical design for strategies to improve the performance of two-dimensional perovskites/C2N in photocatalytic and optoelectronic applications.