The S-scheme heterojunctions effectively boost the charge separation and strong redox capacities. Therefore, designing S-scheme heterojunction systems with improved photocatalytic properties is considered an efficient strategy for solving acute environmental problems. In this study, phosphorus (P) atoms were doped onto g-C 3 N 4 nanosheets via vitamin B 12 (VB12) sources and then decorated with WO 3 nanoplates to form an S-scheme P-CN/ WO 3 heterojunction photocatalyst. The X-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) findings revealed the successful decoration of WO 3 nanoplates on P-CN nanoplates. Also, X-ray photoelectron spectroscopy (XPS) confirmed the doping of P atoms on the g-C 3 N 4 nanosheets. The results from the electrochemical analysis, radical-related experiments, and work function (Φ) further showed the formation of S-scheme heterojunctions with effective interfacial charge transfer. Therefore, the S-scheme P-CN/WO 3 heterojunction material revealed the highest reaction rate constant (0.0185 min −1 ) compared to pure P-CN (0.0061 min −1 ) and WO 3 (0.0041 min −1 ) for degradation of tetracycline (TC) under 30 W light-emitting diode (LED) light irradiation. The response of P-CN and WO 3 to visible light, the defects in the P-CN structure, the proper band gap, and the textural properties resistant against reactive oxygen species (ROS) led to the suitable performance of this photocatalytic system. The current study highlights the industrial manufacture of S-scheme heterojunction catalysts in removing pollutants from wastewater.