The creation of S-scheme heterostructures can overcome the problems of low carrier separation efficiency and reduced redox ability in traditional photocatalysis, and therefore has a wide range of applications in environmental remediation. In this work, a novel highly dispersed Perylene diimide nanoparticles encapsulated BiVO4 nanosheets S‐scheme heterostructure (PTCDI@BVO) was constructed using a simple hydrothermal technique for 2-nitrophenol degradation under visible light irradiation. The optimum 0.3%PTCDI@BVO can degrade 81.06% of 2-nitrophenol within 2 h and presented a high apparent rate constant (0.01413 min−1), which was respectively 14 and 1.8 times higher than that of pristine PTCDI (0.00101 min-1) and BiVO4 (0.00784 min-1). Meanwhile, the optimum sample also demonstrated good cycling performance over five cycles. By adding 200 μL of H2O2, the 2-nitrophenol degradation efficiency can be increased to 96.61%. Moreover, h+ was the primary contributor to the degradation process, followed by •O2- and •OH through the active species trapping tests. The superior photocatalytic activity of PTCDI@BVO has been ascribed to the built of S-scheme heterostructure between 0D PTCDI and 2D BiVO4, which accelerates the carrier transmission and separation efficiency. This study highlights a viable approach for designing and constructing high-performance organic/inorganic S-scheme heterostructures for multiple applications.