An efficient, oxidant and metal-free synthesis of polycyclic heteroaromatic coumarins was developed. H-Furo[2',3':3,4]naphtho[2,1-c]chromen-4-one (2a-2f), 1H-benzofuro[2',3':3,4]naphtho[2,1-c]chromen-1-one (2g-2j), and 4H-thieno[2',3':3,4]naphtho[2,1-c]chromen-4-one (2k-2s) derivatives were obtained by the irradiation of 4-phenyl-3-heteroarylcoumarin in EtOH-H2O (9:1, v/v) using a high-pressure Hg lamp as the light source, at room temperature and under an Ar atmosphere. Owing to the expansion of the π-conjugation system, 2a-2s showed strong fluorescence emissions in ethanol solution ( ΦF = 0.40-0.83).