Herein, an electrochemical approach for the functionalization of alkenes with 1,3-dicarbonyl compounds under oxidative conditions is reported. 1,3-Dicarbonyl compounds undergo single-electron transfer (SET) to generate electrophilic radicals, which upon addition to styrene and aliphatic alkenes afford the 1,2-bifunctionalized and α-alkylated products, respectively. The methodology avoids the usage of external oxidants and shows good tolerance with respect to alkene derivatives.