Mycotoxin contamination poses serious threats to agro-product safety and human health; therefore, exploring green and efficient detoxification strategies is imperative. Photocatalytic techniques, characterized by environmental friendliness, high efficiency, and sustainability, show considerable potential for mycotoxin degradation. This review systematically outlines the fundamental principles of photocatalytic reactions, key factors influencing reaction outcomes, and strategies for technique modification. In addition, advances in the photocatalytic degradation of mycotoxins-including aflatoxin, deoxynivalenol, zearalenone, and patulin-are examined, with emphasis on photocatalyst development, reaction efficiency enhancement, degradation mechanisms, and practical applications. Finally, current challenges and future prospects for photocatalytic mycotoxin degradation are discussed. This review provides theoretical guidance for advancing research on mycotoxin degradation in agro-products.