Selective activation of benzene has been mainly limited to the C-H activation. Simple replacement of one carbon in benzene with another atom remains unresolved due to the high dissociation energy. Herein, we demonstrate a direct breakage of the particularly strong C = C bond in benzene through ion-molecule reaction in a low-temperature plasma, in which one carbon atom was replaced by one atomic nitrogen with the formation of pyridine. The mechanism for the formation of pyridine from benzene has been proposed based on the extensive investigation with tandem mass spectrometry. The reaction pathway also works to other aromatics such as toluene and o-xylene. This finding provides a new avenue for selective conversion of aromatics into nitrogen-containing compounds.