A practical method to synthesize N-heteroaryl esters from N-heteroaryl methanols with acyl cyanides via C–C bond cleavage without using any transition metal is demonstrated here. The use of Na2CO3/15-crown-5 couple enables access to a series of N-heteroaryl esters in high efficiency. This protocol is operationally simple and highly environmentally benign producing only cyanides as byproducts.</p