A N-heterocyclic carbene-catalyzed (NHC) three-component reaction involving N-aminopyridinium salts, alkenes, and aldehydes for the synthesis of β-amino ketones is described. In this reaction, N-aminopyridinium salts and the Breslow intermediate, which is generated from NHC and aldehydes, are utilized to undergo a single-electron transfer process, forming a ketyl radical intermediate and amidyl radicals. Subsequent to the formation of the amidyl radical, it undergoes selective capture by alkenes, followed by radical cross-coupling to yield the desired β-amino ketones.