The magnetic CuFeO₂ anchored on nitrogen-doped porous carbon (CuFeO₂/NC) hybrid catalysts were further synthesized via hydrothermal reaction without the addition of a chemical reductant. The systematic CuFeO₂/NC with larger specific surface areas (SSAs) and abundant active sites exhibited strong adsorption ability and great catalytic performance towards activating peroxymonosulfate (PMS) for sulfamethoxazole (SMX) removal. It was noted that 18 mg/L SMX was completely removed after 40 min of pre-adsorption and 30 min of oxidative degradation in CuFeO₂/NC and PMS system. The degradation rate constant (k) was calculated by fitting as 0.166 min⁻¹, being about 7.9 times that in the CuFeO₂ and PMS system (0.021 min⁻¹). The SO₄·^-,·OH, and ¹O₂ as the dominant reactive oxygen species (ROSs) contributed to sulfamethoxazole degradation. The N species, active oxygen and the redox cycles of Cu(Ⅱ)/Cu(Ⅰ) and Fe(Ⅲ)/Fe(Ⅱ) were confirmed to play a vital role in the activation of PMS for the generation of ROSs. Based on the LC-MS analysis, the possible degradation routes of SMX in the PMS activation system by CuFeO₂/NC were proposed.