Plastics play a crucial role in the survival and advancement of human civilization. However, the increasing challenge of plastic pollution presents significant obstacles. Disposal methods such as incineration and landfilling result in substantial resource wastage and pose potential environmental hazards. The slow progress in recycling and reusing waste plastics hinders their industrial application and effective response to environmental crises. Photocatalysis offers promising solutions for the future of plastic recycling, particularly with the recent increase in photocatalytic degradation methods for polystyrene (PS). This review provides a comprehensive overview of the latest advancements in the photooxidation of PS into high‐value chemicals.