Although the electro-Fenton (EF) process is effective for wastewater treatment, recycling spent catalysts remain a major challenge. Therefore, we introduce a reuse strategy for spent catalysts where an iron hydroxyphosphate [Fe5(PO4)4(OH)3·2H2O] catalyst is utilized. Fe5(PO4)4(OH)3·2H2O obtained •OH and •O2− by activating in-situ produced H2O2, and the degradation rate of sulfamethoxazole reached 94.5% after 120 min and showed excellent stability (maintained above 90%) for 10 cycles. Finally, the used catalyst was converted into slow-release ammonium ferrous phosphate (NH4FePO4·H2O) fertiliser at a conversion rate of 85.6%. NH4FePO4·H2O significantly promoted plant and seed growth within 6 days, highlighting the contribution of the resource recycling of the spent catalyst. This study serves as a valuable reference for the efficient utilization of spent catalysts. This study successfully applied EF catalysts and explored the recycling of spent catalysts.