Regio- and stereoselective synthesis of $N$-substituted azole acrylonitriles has been achieved smoothly in $N,N$-dimethylformamide (DMF) in the presence of potassium carbonate (K$_{2}$CO$_{3})$ 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 $^{1}$H NMR and X-ray crystallography.