We have developed a convenient method for the synthesis of 2-(pyrano[3,2-c]chromen-5-yl)acetic acids and their derivatives. The synthetic approach is based on the ANRORC reaction of chromone-containing acrylic acids and ethyl cyanoacetate. The features of the method are (a) simple reaction conditions (ethanol, 20°C–25°C, triethylamine as catalyst), (b) non-chromatographic isolation of products, and (c) high yields (up to 95%). The resulting pyrano[3,2-c]chromenes have intense fluorescence in the yellow-green region of the spectrum (492–554 nm) and demonstrate large Stokes shifts (up to 6300 cm−1).