Amidines are a preeminent group of organic compounds having wide applications in various industries. Here, we have developed a simple one-step reaction protocol for the facile synthesis ofN-arylamidines catalysed by calcium bis(hexamethyldisilazide) [Ca{N(SiMe3)2}2(THF)2]. The amidine synthesis was readily achieved from organic nitriles and amines which provided a broad substrate scope ranging from electron-withdrawing to electron-donating substitutions as well as heterocyclic substitution. The reaction was carried out in a solvent-free medium under ambient conditions. The nucleophilic addition of aromatic amines to aryl nitriles led to good to excellent yields of the corresponding amidines. The reactivity of the amidines was further examined and the respective urea derivatives were achieved in excellent yields. The plausible mechanism involves the generation of an active calcium amido pre-catalyst that helps in the activation of nitriles in the reaction course. © The Royal Society of Chemistry 2020.