Abstract Absorption and emission spectra of 6,7-dihydroxycoumarin [6,7-DHC] in aqueous solution over a wide pH range are reported. The absorption spectra proved to be strongly sensitive to the pH-value of the solution, whereas the emission spectra change in this range only insignificantly. An interpretation is attempted on the basis of the differences of the acid-base properties of the 6,7-DHC molecule in its ground and excited singlet state. For this purpose the pKa's and pKax's values have been calculated. It has been stated that in the excited state the phototautomer form is very unlikely.