<p>The degradation of antibiotics remains a major and persistent challenge in wastewater treatment. This study reports the synthesis of three distinct catalysts from a zeolitic imidazolate framework-67 (ZIF-67) precursor through pyrolysis at 800&#xa0;°C, namely ZIF-67(Fe)-800, ZIF-67(Co)-800, and ZIF-67(FeCo)-800.&#xa0;Comprehensive characterization (e.g., X-ray diffractometer and transmission electron microscopy analyses) confirmed their graphitic carbon matrix, specific metallic phases, and unique polyhedral morphologies.&#xa0;These catalysts were employed to activate peroxymonosulfate (PMS) for ciprofloxacin (CIP) degradation. Strikingly divergent catalytic performances were observed, with CIP degradation rate constants of 0.0027, 0.0731, and 0.0504&#xa0;min^–1 for ZIF-67(Fe)-800, ZIF-67(Co)-800, and ZIF-67(FeCo)-800, respectively. Furthermore, the bimetallic ZIF-67(FeCo)-800 demonstrated consistently inferior performance in activating both peroxydisulfate and sodium percarbonate compared to PMS, resulting in significantly lower CIP degradation rates of 52% and 87%, respectively. Mechanistic investigations using electron paramagnetic resonance and quenching tests revealed that hydroxyl radical (<b>·</b>OH), sulfate radical (SO₄^•−), and singlet oxygen (¹O₂) were the dominant reactive species in both the ZIF-67(Fe)-800/PMS and ZIF-67(Co)-800/PMS systems. In contrast, the ZIF-67(FeCo)-800/PMS system operated via a distinct pathway, primarily generating SO₄^•−, accompanied by <b>·</b>OH, ¹O₂, and superoxide radicals (O₂^•−). Notably, H₂PO₄⁻ and HCO₃⁻ exhibited strong inhibitory effects on CIP degradation, while SO₄²⁻ and CH₃COO⁻ led to modest rate enhancements. Overall, this work provides a rational framework for designing MOF-derived catalysts and highlights their potential for application in advanced oxidation processes aimed at removing pharmaceutical pollutants.</p>