The development of oxidation processes with the efficient generation of powerful radicals is the most interesting and thought-provoking dimension of peroxymonosulfate (PMS) activation. This study reports the successful preparation of a magnetic spinel of CuFe2O4using a facile, non-toxic, and cost-efficient co-precipitation method. The prepared material exhibited a synergetic effect with photocatalytic PMS oxidation, which was effective in degrading the recalcitrant benzotriazole (BTA). Moreover, central composite design (CCD) analysis confirmed that the highest BTA degradation rate reached 81.4% after 70 min of irradiation time under the optimum operating conditions of CuFe2O4= 0.4 g L−1, PMS = 2 mM, and BTA = 20 mg L−1. Furthermore, the active species capture experiments conducted in this study revealed the influence of various species, including•OH, SO4•−, O2•−,andh+in the CuFe2O4/UV/PMS system. The results showed that SO4•−played a predominant role in BTA photodegradation. The combination of photocatalysis and PMS activation enhanced the consumption of metal ions in the redox cycle reactions, thus minimizing metal ion leaching. Additionally, this maintained the reusability of the catalyst with reasonable mineralization efficiency, which reached more than 40% total organic carbon removal after four batch experiments. The presence of common inorganic anions was found to have a retardant effect on BTA oxidation, with the order of retardation following: HCO3−> Cl−> NO3−> SO42−. Overall, this work demonstrated a simple and environmentally benign strategy to exploit the synergy between the photocatalytic activity of CuFe2O4and PMS activation for the treatment of wastewater contaminated with widely used industrial chemicals such as BTA.