Ce-doped borosilicate (BSG), phosphosilicate (PSG), and borophosphosilicate (BPSG) glasses (B:P:Si molar ratios 8:0:92, 0:8:92, and 8:8:84; Ce:Si molar ratio 1 x 10(-)(4) to 1 x 10(-)(2)) were prepared by the sol-gel method. High-resolution transmission electron microscopy (HRTEM), (31)P, (29)Si, and (11)B magic angle spinning nuclear magnetic resonance (MAS NMR), electron paramagnetic resonance (EPR), and UV-vis absorption investigations demonstrated that, in PSG and BPSG, Ce(3+) ions interact with phosphoryl, [O=PO(3/2)], metaphosphate, [O=PO(2/ 2)O](-), and pyrophosphate, [O=PO(1/2)O(2)](2)(-), groups, linked to a silica network. This inhibits both CeO(2) segregation and oxidation of isolated Ce(3+) ions to Ce(4+), up to Ce:Si = 5 x 10(-)(3). In BSG, neither trigonal [BO(3/2)] nor tetrahedral [BO(4/2)](-) boron units coordinate cerium; thus, Ce(3+) oxidation occurs even at Ce:Si = 1 x 10(-)(4), as in pure silica glass (SG). The homogeneous rare-earth dispersion in the host matrix and the stabilization of the Ce(3+) oxidation state enhanced the intensity of the photoluminescence emission in PSG and BPSG with respect to BSG and SG. The energy of the Ce(3+) emission band in PSG and BPSG matrixes agrees with the phosphate environment of the rare earth.