Photophysical properties of five hydroxyflavones (HF) (some typical models of flavonols), (3 - HF, 6 - HF, 7-HF, 3, 6 - diHF and 3, 7 - diHF) were studied in homogeneous media by means of UV-vis and steady-state and time resolved fluorescence spectroscopies. Their absorption and fluorescence characteristics based on the flavonols structure are presented and discussed. It was found that the fluorescence of the flavonols depends on the nature of the solvent and on their molecular structure, especially on the position and the number of the -OH groups of the substituted phenyl ring. Attention is paid to the number of the -OH groups that influence the excited-state intramolecular proton transfer (ESIPT) process. The fluorescence quantum yield and the lifetime of the flavonols in heterogeneous media have been also determined. The results are discussed with relevance to the flavonols as sensitive fluorescence probe and to their microenvironments in the systems of biological interest and especially in a typical protein environment.