The removal of contaminants of emerging concern (CECs) has become a hot research topic in the field of environmental engineering in recent years. In this work, a simple pyrolysis method was designed to prepare a high-performance biochar-loaded zero-valent copper (CuC) material for the catalytic degradation of antibiotics ENR by PMS. The results showed that 10 mg/L of ENR was completely removed within 30 min at an initial pH of 3, CuC 0.3 g/L, and PMS 2 mmol/L. Further studies confirmed that the reactive oxygen species (ROS) involved in ENR degradation are ·OH, ${\mathrm{S}\mathrm{O}}_4^{-}$·, ¹O₂, and ${\mathrm{O}}_2^{-}$. Among them, ¹O₂ played a major role in degradation, whereas ${\mathrm{O}}_2^{-}$· played a key role in the indirect generation of ¹O₂. On the one hand, CuC adsorbed and activated PMS to generate ·OH, ${\mathrm{SO}}_4^{-}$· and ${\mathrm{O}}_2^{-}$·. ${\mathrm{O}}_2^{-}$· was unstable and reacted rapidly with H₂O and ·OH to generate large amounts of ¹O₂. On the other hand, both the self-decomposition of PMS and direct activation of PMS by C=O on biochar also generated ¹O₂. Five byproducts were generated during degradation and eventually mineralized to CO₂, H₂O, ${\mathrm{N}\mathrm{O}}_3^{-}$, and F⁻. This study provides a facile strategy and new insights into the biochar-loaded zero-valent transition-metal-catalyzed PMS degradation of CECs.