In recent years, with the development of organic synthetic chemistry, a variety of organic synthetic methods have been discovered and applied in practical production. Photochemistry and electrochemistry have been widely used in organic synthesis recently due to their advantages such as mild conditions and green and environmental protection and have now been developed into two of the most massive synthetic strategies in the field of organic synthesis. In order to further enhance the potential of photochemistry and electrochemistry and to overcome the limitations of each, organic synthetic chemists have worked to combine the two synthetic strategies together to develop photoelectrochemistry as a new synthetic method. Photoelectrochemistry achieves the complementary advantages and disadvantages of photochemistry and electrochemistry, avoids the problem of using stoichiometric oxidants or reductants in photochemistry and easy dimerization in electrochemistry, generates highly reactive reaction intermediates under mild conditions, and achieves reactions that are difficult to accomplish by single photochemistry or electrochemistry. This review summarizes the research progress in the field of photoelectrochemistry from the perspective of photoelectro-chemical catalysts in recent years, analyzes the catalytic mechanism of various catalysts in detail, and gives a brief outlook on the research direction and development prospects in this field.