Vicinal　diamines　are　an　important　structural　motif　that　has　been　widely　used　in　biological,　medicinal,　and　materials　science.　Transition-metal-catalyzed　diazidation　of　alkene　is　a　straightforward　and　efficient　approach　for　vicinal　diamines,　which　are　unfavorably　associated　with　excess　oxidants　and　limited　substrate　scope　for　electron-deficient　alkenes.　Herein　we　report　an　electrocatalytic　diazidation　of　alkenes　with　the　electrode　coated　by　Cu　nanoparticles　pyrolyzed　from　Cu(salen)-based　metal-organic　framework.　This　strategy　is　compatible　with　various　alkenes　including　those　electro-deficient　ones.　Remarkably,　the　modified　electrode　maintains　high　electrocatalytic　activity　for　diazidation　even　after　15　cycles.　©　2025　Elsevier　Ltd