We report here a general alkylation reaction of terminal alkenes with nucleophilic cobaloxime complex catalysis under visible light irradiation. A broad range of vinyl arenes and heteroarenes, as well as a diverse set of alkyl(pseudo)halides or strained rings as alkyl electrophiles, can efficiently undergo the transformation up to the gram scale. Mechanistic study reveals the radical nature of the reaction and corroborates our design involving alkylcobaloxime as the key intermediate.