New atom-economic and environmentally friendly processes should replace the traditional ways of building C–C, C–N, C–O, C–P, C–S bonds, which are usually based on the replacement of a halogen atom, and, therefore, required the preliminary modification of substrates, and the use of aggressive reagents, harsh conditions or expensive catalysts. In recent years, the direct metal-free functionalization of the C(sp2)–H bond, which provides the most efficient and low-waste pathway for molecular transformation, has attracted increasing attention. However, these transformations usually require stoichiometric amounts of chemical oxidizing agents. The modern world and its sustainable development trends are forcing the chemical industry to improve in an environmentally friendly direction and meet the requirements of “green chemistry.” In this regard, the use of electrochemical methods is extremely important. Electrochemical anodic oxidation is an ideal option for the replacement of chemical oxidizers in C–H functionalization reactions. The data on the main electrochemical methods and approaches used for the direct functionalization of the C(sp2)–H bond in heterocyclic compounds are classified and summarized in this paper.