This paper describes the processing of rare-earth/organic dye composites fabricated via three different sol-gel routes. In the first approach, low hydroxyl ormosil matrices were fabricated via reaction of a methyl-modified silicon halide with tertiary alcohol and subsequently doped with erbium iodide and a near-infrared dye. In the second approach, gels were made from tetramethoxysilane and doped with erbium complexes and dyes. In the third approach, a hybrid siloxane method was used. No Er3+ luminescence at 1.55 mm was observed in any of the three cases, mainly due to the strong absorption of the matrices centered around 1.4 mm. Fluorescence of Er3+ in the visible was observed in the first matrice, but no dye luminescence was detected. Dye luminescence was observed in the second type matrix, along with some reabsorption of the dye luminescence by Er3+. In the third approach, neodymium exhibited optical activity in the near infrared, as well as the dye.