Functionalized S-aryl thioimidates were synthesized from thioamides and arylboronic acids at room temperature under mild conditions. The reaction was catalyzed by copper(II) acetate in the presence of DBU under an open atmosphere. A wide range of functionalized aryl and alkyl boronic acids was chemo-selectively coupled with aryl and alkyl thioamides to obtain corresponding S-aryl and S-alkyl thioimidates in 64-80% yields. Room temperature reactions, easy operation, and broad substrate scope are the salient features of the developed methodology.