The optical spectroscopy of the europium ion has been used as a probe of the structural changes occurring as a function of processing temperature in sol-gel derived glasses. The fluorescence and fluorescence decay times of the EuJ' ion were observed and changes in the emission spectra and decay measurements were interpreted in terms of the changes taking place within the sol-gel matrix. Measurements of the fluorescence decay time indicate abnormally short lifetime measurements for sol-gel derived glasses even at relatively high fabrication temperatures. This was construed as being due to residual OH groups remaining in the glass structure Measurements also indicated the presence of a fast lifetime component superimposed upon the slower decay of the Eu1* ion. This was interpreted as concentration quenching because of rapid energy transfer within clusters of the dopant europium ion.