Herein, we report a solvent-controlled highly selective amidation and imidation of aroyl chlorides using an alkali-metal silyl-amide reagent (LiHMDS), which serves as a nitrogen source at room temperature. A unique feature of this method lies in the sequential silyl amidation of aryol chlorides and nitrogen–silicon bond cleavage of the corresponding N,N-bis(trimethylsilyl)benzamide in a one-pot method in a very short reaction time. This effective strategy was extended to late-stage functionalization.