Aluminosilicate gels containing photochromic spiro(1,3,3-trimethylindolo-2,3’-naphth[1,2-b]-1,4-oxazine) were prepared by the sol-gel route. The spirooxazine compound has been used as a photochromic probe for studying the sol to gel transitions of aluminosilicate host gels. Absorption and luminescence spectroscopy were used to elucidate physicochemical changes to the gel network. The photochromic probe compound was found to be very sensitive to local changes that occur during the gel formation process.