A novel electrochemical procedure for the one-pot synthesis of variously substituted 5-thiotetrazole has been established by a three-component reaction (thiol(thiophenol)s, isocyanides, and azidotrimethylsilane). This approach is achieved by the sulfidation of isocyanide and subsequent cycloaddition with azidotrimethylsilane under mild conditions without a metal catalyst or external oxidant. Importantly, the presented methodology not only features a wide substrate scope but also exhibits the practicality showcased by gram-scale synthesis and various conversions.