We present results of fluorescence line narrowing (FLN) and lifetime studies of Eu3+-doped ormosils prepared from Si(OCH3)4 and CH3Si(OCH3)3, (CH3)2Si(OCH3)2, (C2H5)2Si(OCH3)2, and (n-C3H7)Si(OCH3)3 in various proportions. Similar results are also presented for Eu3+-doped gels derived from Si(OCH3)4 and fluorinated Eu3+ precursors (Eu(fod)3, (CF3SO3)3Eu, and (CF3CO2)3Eu·3H2O). The FLN studies indicated that significant Eu3+ clustering occurs in densified samples of both the organically modified and fluorinated compositions. Lifetime studies of the organically modified compositions showed longer Eu3+ lifetimes at low heat treatment temperatures relative to an unmodified sample. The difference in lifetime between modified and unmodified compositions decreased at high heat treatment temperatures as the organic substituents were driven from the matrix. The longest Eu3+ lifetimes were observed when the fluorinated Eu3+ precursors were used and persisted at high heat treatment temperatures. The lifetime studies indicate that the fluorinated precursors, and to a lesser extent organically modified precursors, are effective at reducing the water content in densified gels.