A series of 2-amino-4-aryl-5-oxo-4,5-dihydropyrano[3,2- c]chromene derivatives has been synthesised by the reaction of 4-hydroxycoumarin and substituted cinnamonitriles catalysed by KF-montmorillonite. The structures were characterised by IR and 1H NMR spectroscopic data and confirmed by X-ray diffraction analysis.