The fluorescence spectra of 9-anthrol during the sol-gel-xerogel transitions of 13 systems containing different silicon and aluminum ratios and catalysts have been observed at a constant temperature (300 K) as a function of the sol-gel reaction time. Fluorescence decay curves for typical xerogel samples also have : been observed. 9-Anthrol in the sol-gel systems showed four different fluorescence bands originating from the hydrogen-bonded, the complex, the ion pair, and the anion form species. Continuous light irradiation of the xerogels at 360 nm led to an increase in the fluorescence at 480 nm. These findings indicate that anthrone transforms to 9-anthrol by the photoinduced intermolecular proton transfer in these matrixes. The most effective and remarkable tautomerization occurred in the Si:Al=90:10 system, and it was concluded that this photochromic behavior occurs by the photoinduced proton transfer from a proton at the surface Bronsted acid site on the -O-Si-O-Al-O- network to the anthrone molecule.