An efficient and valuable N–N dimerization reaction of N-alkoxyamides is reported under undivided electrolytic conditions. This electrochemical strategy provides a powerful way to access a wide range of advanced, highly functionalized hydrazines. Remarkably, an N-centered radical generated from the cleavage of the N–H bond under electrolytic conditions plays a crucial role in this transformation. Furthermore, various N-alkoxyamides bearing different substituents are suitable in this transformation, furnishing the corresponding hydrazines in up to 92% yield.