Electrochemical strategies have been a powerful approach for the synthesis of valuable intermediates, in particular heterocyclic motifs. Because of the mild nature, a wide range of nonclassical bond disconnections have been achieved via in situ-generated radical intermediates in a highly efficient manner. In particular, anodic electrochemical oxidative strategies have been utilized for the total synthesis of many structurally intriguing natural products. In this review article, we have discussed a number of total syntheses of structurally intriguing alkaloids and terpenoids in which electrochemical processes play an important role as a key methodology.