Ethyl 2-[(2-amino-3-cyano-4-phenethyl-4 H-naphtho[1,2- b]pyran-8-yl)oxy]acetate has been synthesised by condensation of ethyl 2-chloroacetate with the hydroxy group of 2-amino-8-hydroxy-4-phenethyl-4 H-naphtho[1,2- b]pyran-3-carbonitrile. The latter was prepared from cinnamaldehyde, malononitrile and naphthalene-1,6-diol through Knoevenagel condensation and cyclisation reaction and then reduction with hydrogen in the presence of Pd/C at room temperature. The crystal structure of the title compound was determined. In addition, the compound showed distinct inhibition of the proliferation of some cancer cell lines.