A simple procedure for the copper‐catalyzed synthesis of 3‐(N‐heteroaryl)acrylonitriles was developed. Using a combination of Lewis and Brønsted acids, this one‐pot procedure undergoes via a radical conjugated addition and dehydration processes, without isolation of any intermediate, affording the acrylonitriles. This diastereoselective approach allowed the synthesis of a broad scope of quinazoline derivatives (22 examples) with moderate to good yields and good functional‐group tolerance and could be extended to other N‐heterocyles such as quinolines and isoquinolines. Based on control experiments, a mechanistic proposal for this new transformation is also presented.