The　widespread　use　of　tetrazoles　in　medicine,　biology,　and　materials　science　continuously　promotes　the　development　of　their　efficient　and　selective　syntheses.　Despite　the　prosperous　development　of　multicomponent　reactions,　the　use　of　the　most　abundant　and　inexpensive　chemical　feedstocks,　i.e.,　alkanes　and　alkenes,　toward　the　preparation　of　diverse　tetrazoles　remains　elusive.　Herein,　we　developed　an　electrochemical　multicomponent　reaction　(e-MCR)　for　highly　efficient　and　selective　C-H　tetrazolation　of　alkyl　arenes.　When　applied　to　alkenes,　the　corresponding　vicinal　azidotetrazoles　were　readily　obtained,　which　were　further　demonstrated　to　be　versatile　building　blocks　and　potential　high-energy　materials.　©　2022　The　Royal　Society　of　Chemistry.