The development of oxidation processes with generating powerful radicals is the most interesting and thought-provoking dimension of peroxymonosulfate (PMS) activation. In this study, a magnetic spinel CuFe2O4 was successfully prepared by a facile, non-toxic, cost-efficient co-precipitation method with the synergetic effect of photocatalytic PMS oxidation against recalcitrant benzotriazole (BTA) pollutant. The high particle dispersion and large surface area (201.898 m2/g) provided a high photocatalytic activity with CuFe2O4. The obtained results from the central composite design (CCD) analysis confirmed the optimum degrading rate of BTA reached 81.4% at the optimum operational condition of CuFe2O4= 0.4 g/L, PMS= 2 mM, BTA= 20 mg/L after 70 min irradiation time. As such, the active species capture experiments revealed the presence of •OH, SO4•‒, O2•‒ and h+ species in CuFe2O4/UV/PMS system where SO4•‒ was dominated for BTA photodegradation. The combination of photocatalysis and PMS activation enhanced the consumption of metal ions in redox cycle reactions, thus preventing metal leaching and maintain the recyclability with reasonable mineralization efficiency which achieved more than 40% total organic carbon removal after four batch experiments. A retardant effect on BTA oxidation was observed with comparing the water’s common anion constituents as HCO3‒ > Cl‒ > NO3‒ > SO2‒. Results from intermediates identification showed that the transformation pathway of BTA developed as the deprotonation, hydrolysis and ring cleavage processes promoting the practical potential of photo-absorbing CuFe2O4 catalyzed PMS which can be a promising method due to convenient magnetic separation form the solution.