Vicinal diamines are an important structural motif in bioactive natural products and pharmaceutical intermediates. Herein, an environmentally friendly and efficient electrochemical approach to azidoacetamides, as one variant of vicinal diamines, has been developed. This reaction features mild conditions and broad substrate scope, without the use of any chemical oxidant or transition-metal catalysts. The obtained vicinal azidoacetamides could be conveniently converted into various other vicinal diamine derivatives.