MOF-based photoelectrocatalysis (PEC) using CO2 as an electron donor offers a green, clean, and extensible way to make hydrocarbon fuels under more tolerant conditions. Herein, basic principles of PEC reduction of CO2 and the preparation methods and characterization techniques of MOF-based materials are summarized. Furthermore, three applications of MOFs for improving the photoelectrocatalytic performance of CO2 reduction are described: (i) as photoelectrode alone; (ii) as a co-catalyst of semiconductor photoelectrode or as a substrate for loading dyes, quantum dots, and other co-catalysts; (iii) as one of the components of heterojunction structure. Challenges and future wave surrounding the development of robust PEC CO2 systems based on MOF materials are also discussed briefly.