Fe-based heterogeneous catalytic advanced oxidation processes show great potential for treating wastewater. However, catalyst instability often hinders their practical use, mainly due to the slow regeneration of Fe²⁺ sites. Herein, we developed a Fe₃S₄/WO₃ catalyst, where the electron-rich Wx and Sx sites promoted efficient electron transfer, enabling continuous regeneration of Fe²⁺ active sites on the catalyst surface. The Fe₃S₄/WO₃ catalyst exhibited outstanding degradation efficiency for tetracycline (TC) in the peroxymonosulfate (PMS) system, achieving a 92.5% removal efficiency, significantly higher than its individual components of Fe₃S₄ (52.8%), WO₃ (43.1%), and WS₂ (53.2%). Moreover, the Fe₃S₄/WO₃/PMS system demonstrated a broad operational pH range (3.0–9.0), excellent degradation efficiency for various emerging pollutants, minimal interference from background electrolytes and organic matter, and strong stability in real water treatment. Chemical scavenger tests and electron paramagnetic resonance (EPR) analysis confirmed that the oxidative degradation of TC was driven by multiple reactive species, including SO₄^•−, ^•OH, ^•O₂⁻, and ¹O₂. This study provides a novel strategy for regulating active sites in Fe-based catalysts to ensure sustained performance, offering a pathway for the rational design of next-generation Fenton-like catalysts for efficient and sustainable micropollutant removal from wastewater.