Constructing high-efficiency heterostructured photocatalysts for antibiotic degradation is critical and challenging. Herein, a “pearl necklace” α-MnO₂@CoS₂ photoelectrode was prepared via a continuous hydrothermal process. The as-obtained photoelectrode comprised overlong α-MnO₂ nanowires (as leading wire) and CoS₂ nanocages (as decorations) derived from ZIF-67 precursor. The contrivable α-MnO₂@CoS₂ photoelectrode exhibited lower charge transfer resistance and higher carrier separation efficiency than single α-MnO₂. The α-MnO₂@CoS₂ provided a heterostructured interface with fast carrier transfer, where α-MnO₂ nanowire played the carrier transfer channel, and the CoS₂ “nanocages” can effectively increase the contact area between the catalyst and the pollutants. Meanwhile, the stable p-n junction with the internal electric field can be formed in the synthesized α-MnO₂@CoS₂ composite to avoid the destruction of heterogeneous junctions and thus maintain stability. As a result, the α-MnO₂@CoS₂-0.2 had the highest PEC efficiency with a degradation rate of 98.95% for sulfonamides (SMX) within 50 min among prepared catalysts. The charge density difference of α-MnO₂@CoS₂ was performed to investigate the strong interaction between α-MnO₂ and CoS₂. This study provides insights into the construction of nanomaterial structures and their applicability to photocatalytic degradation of target pollutants, which can be expanded for future cost-effective water purification applications.