By exploiting electron donor-acceptor (EDA) complexes between 1,4-dihydropyridines and N-amidopyridinium salts under visible light irradiation, we discovered that photoinduced intermolecular charge transfer induces a single-electron transfer event without requiring a photocatalyst for the facile functionalization of pyridines. The generality of this method is amenable to various types of 1,4-dihydropyridines radical precursors to generate structurally different radicals such as alkyl, acyl, and carbamoyl radicals, ultimately providing facile access to synthetically valuable C4-functionalized pyridines. A broad range of functional groups are well accommodated under mild and metal-free conditions, and the synthetic utility of the present method is showcased by the late-stage functionalization of a variety of biologically relevant pyridine-based compounds, pharmaceuticals, and peptide feedstocks.