<p>This study developed a synergistic treatment system based on nano-ZnFe₂O₄ activated peroxymonosulfate (PMS), which can realize efficient simultaneous removal of refractory P(III)-Ni(II) complexes from electroless nickel plating wastewater via a surface-confined oxidation-adsorption mechanism. Isotherm experiments at 25 ℃ and pH 6 demonstrated that the ZnFe₂O₄/PMS/P(III)-Ni(II) system achieved maximum adsorption capacities of 0.56 mmol/g for total phosphorus (TP) and 0.31 mmol/g for Ni, as derived from the Sips and Langmuir models, respectively. Kinetic analysis revealed that TP removal followed pseudo-second-order kinetics, whereas Ni removal adhered to pseudo-first-order kinetics. The introduction of PMS significantly enhanced adsorption capacity, with the equilibrium TP adsorption in the ZnFe₂O₄/PMS/P(III) system increasing by 109.1% and 64.3% compared to the ZnFe₂O₄/P(III) and ZnFe₂O₄/P(V) systems, respectively. Ni(II) participated in PMS activation to generate Ni(III), resulting in a 60.9% higher TP removal rate in the ZnFe₂O₄/PMS/P(III)-Ni(II) system than in the ZnFe₂O₄/PMS/P(III) system. Quenching experiments identified singlet oxygen as the dominant reactive oxygen species, which oxidized P(III) to P(V) via a non-radical pathway. XPS further confirmed the in situ immobilization of P(V) through M-O-P bonding. The phosphorus removal exhibited strong anti-interference capability, maintaining high TP removal efficiency across a wide pH range (3–9) and in the presence of coexisting ions. ZnFe₂O₄ retained over 92% of the TP removal after five cycles in the recycling tests. This study provides a novel strategy for advanced treatment of complex electroplating wastewater.</p>