Against the backdrop of escalating antibiotic pollution, this study presents a novel approach to remediation using a photothermal heterogeneous Fenton‐like catalyst, Bi12CoO20/rGO, which efficiently activates peroxymonosulfate (PMS) under near‐infrared (NIR) light. This catalyst capitalize on the NIR absorption capabilities of Bi12CoO20 and the electron transfer properties of reduced graphene oxide (rGO). The restored sp2 structure of rGO serves as a conduit for electron transfer, crucial for the redox cycle of Co2+/Co3+ that facilitates PMS activation. Moreover, the incorporation of rGO significantly boosts the NIR absorption capacity of Bi12CoO20, thereby enhancing the photothermal conversion efficiency of the composite and further promoting PMS activation. This synergy enables efficient light‐to‐heat conversion and PMS activation, generating reactive oxygen species (ROS) essential for antibiotic degradation. Using levofloxacin (LVX) as a representative pollutant, the developed system achieves an impressive 99% degradation rate within just 30 min under Bi12CoO20/rGO + PMS + NIR conditions. Moreover, this approach demonstrates robust stability and adaptability across diverse water compositions and pH ranges. Its eco‐friendly nature and renewable characteristics position it as a promising solution for combating antibiotic pollution through photothermal Fenton‐like technology, thereby harnessing solar energy for environmental remediation and fostering sustainable water management practices.