Photoelectrochemical cerium catalysis is an emerging and rapidly developing organic synthetic strategy. By combining the concerted energy transfer from light and electricity to cerium, with the ligand-to-metal charge transfer of excited state CeIV species, a sustainable platform is built. With this powerful strategy, hard to be oxidized substrates can be activated in a mild condition, contributing to broad functional group compatibility. Such as, carboxylic acids, alcohols and Cl anion can deliver corresponding radicals via formal single electron transfer (SET) with a low oxidation potential. Further cooperation with other synthetic strategies including alkoxy radical promoted hydrogen atom transfer (HAT) and β-scission, inert C(sp3)-H, Si-H and C-C bonds can be functionalized via a mild radical pathway. In this review, the recent advances of photoelectrochemical cerium catalysis are described. More importantly, due to this field features some unique advantages, but is rarely explored, we hope chemists will pay more attention on this catalytic system. 1 Introduction 2 Activation of carboxylic acids 3 Activation of alcohols 3.1 Alkoxy radical involved hydrogen atom transfer 3.2 Alkoxy radical promoted β-scission 4 Formal single-electron oxidation of Cl anion 5 Conclusions and Outlook