An efficient electrophilic amidomethylation of aromatics was described to construct N-benzylic amides, which are core structures in drugs and natural products. The simple combination of dimethyl sulfoxide (DMSO, as the CH₂ unit) and acetonitrile (MeCN, as the nitrogen unit) as a highly active amidomethylation reagent enables the efficient C–C, C–N and CO bond construction. Notably, this method provides a practical protocol for the efficient preparation of deuterated benzylamine derivatives with easily available d₆-DMSO or d₃-MeCN, and is also applied in the concise synthesis of Nonivamide and Pimavanserin.