A fluorescent silicone network was prepared by a hydrosilylation reaction using poly(dimethylsiloxane-co-methyl-hydrogensiloxane) terminated by dimethylhydrogensilyloxy groups, poly(dimethylsiloxane-co-methylvinylsiloxane) terminated by dimethylvinylsilyloxy groups and 9-vinylanthracene, as the fluorescent group. These silicone-based materials were strongly fluorescent. Steady state emission was a convenient technique to prove that reaction occurred, based on the blue-shift of the emission from anthracenyl moieties compared with the 9-vinylanthracene. Thermal transitions were studied by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and by fluorescence spectroscopy, indicating that networks with and without lumophores had similar thermal properties. Networks with and without lumophores had the same swelling capability in toluene. Fluorescence spectroscopy was a more sensitive technique to the onset of the glass transition temperature (T = 145 K) than DSC or DMA. Nevertheless, the crystallization temperature at 192 K was determined more precisely by DSC, and the melting point at 237 K was indentified more clearly by both DSC and DMA. These three techniques provided complementary information about transitions in silicone networks. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 74-81, 2010