Emerging analytical technologies are being developed to provide advanced methods for monitoring 4-chlorophenol (4-CP) in the environment. Herein, a label-free, sensitive, and rapid photoelectrochemical (PEC) 4-CP detection system was constructed based on ternary composites of Ag nanoparticles, graphitic carbon nitride (GCN) and carbon spheres (CS) (Ag/GCN/CS). The proposed ternary composites were synthesized by a simple hydrothermal method. In this process, ascorbic acid (AA) played a crucial role in reducing Ag+ to metallic Ag, and provided a carbon source for CS. Due to synergistic promotion by the surface plasmon resonance (SPR) effect of Ag nanoparticles and electron-transfer behavior of CS, the ternary composites exhibited a broad visible light response and fast charge transfer, leading to a tremendously enhanced PEC response. Based on the promotion of the PEC response, a PEC sensor for 4-CP was designed by detecting the photocurrent signals of the PEC electrode after adding 4-CP to solution. Under optimal conditions, the PEC sensor exhibited a wide linear range for 4-CP from 16 to 1104 ng mL(-1), with a limit of detection (LOD) of 5.33 ng mL(-1). In particular, the present work may assistance in better understanding the synergistic effect between the SPR effect of Ag nanoparticles and electron transfer properties of CS. The results can also be applied to other PEC and photocatalytic systems in conjunction with high-performance photoactive materials.