A series of unexpected pyrimidine spiro-benzoquinolines were developed based on the reaction of N-(arylidene)naphthalen-2-amine, arylaldehyde, 1,3-dimethylbarbituric acid in aqueous media catalyzed by triethylbenzylammonium chloride (TEBAC). The structure of the product 4a was confirmed by X-ray diffraction studies. In addition, the water was chosen as green solvent.