Regio- and stereoselective synthesis of N-substituted azole acrylonitriles has been achieved smoothly in N, N-dimethylformamide (DMF) in the presence of potassium carbonate (K2CO3) as a base catalyst. N-Substituted azole acrylonitriles were obtained in moderate to good yields (39% 87%) with a one-pot reaction between readily available N-acetylazoles and Baylis-Hillman nitriles. The structural determinations were accomplished by NOESY H-1 NMR and X-ray crystallography.