A three-component alkene alkylazidation using sodium azide as the azido resource and heteroarenium salts as functionalized alkyl reagents for producing highly valuable 2-azido-1-(1,4-dihydropyridin-4-yl)-ethanes is described. This reaction allows the incorporation of both an azido group and a 1,4-dihydropyridin-4-yl group across CC bonds to construct two new bonds in a single reaction step, and represents a practical and mechanistically distinct alternative that harnesses an electrophilic heteroarenium ion to accomplish the alkene difunctionalization reaction.