In this work, CeMn_1-xM_xO₃ (M = Cu, Fe and Co) perovskites were synthesized and used as efficient heterogeneous catalyst for degrade of tetracycline chloride (TC-HCl) via photocatalysis coupled peroxymonosulfate (PMS) oxidation under visible-light illumination. Metal doping significantly improved the catalytic activity of perovskites. The CeMn_0.6Co_0.4O₃/PMS/Vis system demonstrated excellent performance that 96.4% of 60 mg/L of TC-HCl was degraded within 30 min with a high reaction rate constant of 0.136 min⁻¹, which is about 4.3 times higher than that of CeMnO₃, and almost 4.4 times higher than that of pure PMS. Results confirmed the addition of Co led to mixed valence states of Mn (III)/Mn (Ⅳ) and Co (II)/Co (III) in the perovskite structure, promoting the electron transfer from the CeMn_0.6Co_0.4O₃ to PMS. Moreover, CeMn_0.6Co_0.4O₃ exhibited good stability over a wide pH range (3.0–11.0). The rapid transformation of Co (II)/Co (III) redox pairs is critical for PMS activation as the limiting step. Superoxide radicals (•O₂⁻), electron (e⁻) and sulfate radical (SO₄⁻•) were the dominant oxidative species responsible for removing TC-HCl. This work proposed some new insights to understand the heterogeneous reaction mechanism during PMS oxidation and photocatalytic process and promote the development of perovskites catalyst for removal of organic pollutants.