Visible-light-induced difunctionalization of alkenes is a powerful strategy for constructing complex molecules. Herein, we disclose a three-component 1,2-alkylpyridylation of alkenes under mild and photosensitizers-free conditions. UV-vis absorption spectroscopy studies and NMR titration experiments indicate that the formation of an EDA complex between 4-alkyl-DHPs and 4-cyanopyridines. Primary, secondary, and tertiary C(sp3)-centered radicals were formed by homolytic cleavage of 4-alkyl-DHPs. Gram-scale synthesis and late-stage functionalization of medicinally relevant molecules showed the synthetic potential of our methodology.