6-Propionyl-2-(dimethylamino)naphthalen (PRODAN) is an extremely solvent sensitive probe. Changes in its photophysical characteristics are used to probe the microenvironment of the sol-gel matrix as a function of aging time. These results clearly demonstrate that PRODAN senses a distribution of microenvironments within the sol-gel matrix. The ensemble of domains are evident immediately after gelation up until the drying stage. The extent of this microheterogeneity varies as a function of aging time. Steady-state emission anisotropy and time-resolved emission data provide detailed information on how the various stages of the sol-gel process affect the photophysics of PRODAN.