Broadband fluorescence and fluorescence line narrowing (FLN) spectra are presented for Eu3+ ions in Eu2O3-SiO3 and Eu2O3-Al2O3-SiO3 systems prepared by the sol-gel process. Clustering of rare earth ions in silica glass can be a limiting factor in the design and engineering of optical device materials. The addition of Al2O3 is known to help disperse rare earth ions in sol-gel silica. In order to develop a more detailed understanding of how Eu3+ is incorporated in these materials, time-resolved, laser-induced FLN studies at 77 K have been performed using a pulsed dye laser to selectively excite subsets of ions in the inhomogeneously broadened 7F0⇆ 5D0 manifold. Fluorescence spectra are discussed in terms of rare earth ion clustering, energy transfer, and bonding site symmetry. It is concluded that Eu3+ ions cluster in sol-gel silica and that the addition of alumina assists in dispersing Eu3+ ions.