The scientific analysis of food safety issues and the establishment of rapid and efficient food safety detection methods are of great significance for safeguarding the health of consumers, ensuring the healthy development of food safety systems and realizing food safety strategies. As an emerging electrochemical analysis technology, photoelectrochemical (PEC) biosensors, which combine the advantages of biological analysis and optical analysis, have attracted extensive attention. Due to the complete separation of the excitation source (light) and the detection signal (current), the background signal of PEC biosensors is greatly decreased, and their sensitivity is high. The detection principle is that under illumination, the biological recognition effect between the bio-specific recognition element and the corresponding target causes a change in the signal generated by the photoactive nanomaterial. This review aims to cover the most recent advances of PEC biosensing in the field of food analysis, including mycotoxins, heavy metals, antibiotics, and pesticide residues. The future prospects in this field are also discussed.