The electrochemical C‐H hydroxylation and alkoxylation reactions have emerged as sustainable platforms to construct valuable oxygenated compounds such as alcohols, phenols, and ethers. Compared with traditional approaches, these electrochemical strategies not only enhance the atom economy through bypassing the use of chemical oxidants but also unlock new reactivities by accessing reactive intermediates under mild conditions. In this review, we tried to provide an overview of the representative achievements in this field since 2020. The related transformations are classified into five parts according to the underlying mechanisms. Furthermore, the potential opportunities and challenges within this rapidly emerging field were also discussed. This review is not intended to be exhaustive but rather to illustrate the synthetic potential of electrochemical C‐H hydroxylation and alkoxylation strategies in the sustainable and selective assembly of valuable oxygenated compounds.