Time‐resolved site‐selection spectroscopy techniques using a pulsed tunable dye laser were used to investigate the spectral structure and dynamics of Eu3+ions in six oxide and one fluoride glass hosts. Network modifier ions were found to be important in determining the details of the spectral structure which can be related to the amount of local order in the glass. As the relative order increases, the fluorescence lifetime was found to decrease and the energy transfer rate increase. The transfer rate was found to vary linearly with the predicted ion‐ion interaction rate for the oxide glasses. Differences in the temperature and excitation wavelength dependences of the energy transfer rates were found for the different samples.