In this paper, a new series of ethyl 1-aryl-3-methyl-8-oxo-1,8-dihydropyrano[2′,3′:4,5]pyrimido[6,1-b]quinazoline-2-carboxylate derivatives was synthesised by the cyclisation of methyl anthranilate with ethyl 5-cyano-6-[(ethoxymethylene)amino]-2-methyl-4-aryl-4H-pyran-3-carboxylate derivatives, which were obtained from reaction of triethyl orthoformate with 6-amino-5-cyano-2-methyl-4-aryl-4H- pyran-3-carboxylate derivatives. The title compounds possessed good fluorescence properties. In addition, ethyl 5-cyano-6-[(ethoxymethylene) amino]-2-methyl-4-(p-tolyl)-4H-pyran-3-carboxylate and ethyl 3-methyl-8-oxo-1-(p-tolyl)-1,8-dihydropyrano[2′,3′:4,5]pyrimido[6,1-b] quinazoline-2-carboxylate were further determined by single crystal X-ray diffraction analysis.