An electrochemical protocol for benzylic C(sp3)-H aminopyridylation via direct C-H/N-H cross-coupling of alkylarenes with N-aminopyridinium triflate has been developed. This method features excellent site-selectivity, broad substrate scope, redox reagent-free and facile scalability. The generated benzylaminopyridiniums can be readily converted to benzylamines via electroreductive N-N bond cleavage.