A catalyst-free approach for the multicomponent aminoheteroarylation reaction of alkenes with N-aminopyridinium salts and heteroarenes is herein described. The reaction shows good functional group tolerance and allows the generation of valuable β-heteroarylethylamines in satisfying yields. In this transformation, N-aminopyridinium salts and heteroarenes are utilized to generate electron donor–acceptor complexes, which undergo a single-electron transfer process upon light irradiation to form key amidyl radicals and heteroaryl radical cations. The amidyl radical is subsequently captured by alkenes, followed by a Minisci-type reaction to yield the desired β-heteroarylamines as products.