Developing cost‐effective and efficient photo‐Fenton catalysts is crucial for advancing photo‐Fenton technology. MoS2 is a representative transition metal disulfide with attractive photoresponsiveness, making it ideal for preparing composite photo‐Fenton catalysts. In this study, natural molybdenite was innovatively utilized as a source of MoS2 (OM) to synthesize a low‐cost and efficient Fe@MoS2 (OMF) composite photo‐Fenton catalyst by comminution and adsorption, which was then applied to the remediation of antibiotic‐contaminated water. The OMF composites exhibited significant catalytic activity, with a kinetic rate constant of 0.022 min−1, which was 3.1 times higher than that of the original OM (0.007 min−1), indicating a 3% increase. This was attributed to the synergistic effect of many photogenerated electrons and reversible Mo4+/Mo6+ redox pairs, which accelerated the regeneration of Fe2+. After three cyclic tests, the concentrations of dissolved Fe2+ and Mo2+ ions remained below 0.38 mg/L and 0.17 mg/L, respectively. This indicates the high reusability of the catalyst in cyclic experiments. Ultimately, the main active species, •OH and •O2−, were generated during the photo‐Fenton process, contributing significantly to TC degradation. This study may serve as a reference for the development and application of natural mineral composite photo‐Fenton catalysts in the treatment of organic wastewater.