A transition-metal-free approach for the preparation of N-arylketimines has been developed from the direct reaction of aryldiazonium salts, arenes, and nitriles in a one-pot fashion with the consecutive formation of N-C and C-C bonds. This approach proceeds via an in situ generation of N-arylnitrilium intermediate, which then undergoes intermolecular arylation. This three-component strategy offers a step- and atom-efficient way to N-arylketimines from easily accessible reagents under mild reaction conditions. The characterization of stereochemistry of ketimine was achieved by X-ray crystallographic structure and theoretical calculation. Operational simplicity, shorter reaction time, excellent functional group compatibility, and scalability are the key features of this report.