Tin oxide-silica composite aerogels were successfully prepared with a co-fed precursor sol-gel process. The crystallinity of the tin oxide nanoparticles, embedded in the mesoporous SiO2 network, was improved with increasing the post-reaction thermal treatment temperature. The composite aerogels exhibited a rich photoluminescence (PL) emission contributed by both SnO2 and SiO2. The PL peak of 346 nm was from the near band edge emission of the tin oxide nanoparticles, and the ones located at 310 and 476 nm were attributable to the oxygen deficiencies of the silica network. Three more emission peaks, 387, 432, and 522 nm, were observed, with the 387 nm peak contributed by the oxygen vacancies Vo(++), the 432 nm peak by the Sn interstitials, and the 522 nm peak by the oxygen vacancies Vo(+), respectively, of the tin oxide nanoparticles. The intensities of these three defect level emissions were found decreased, as compared to that of the near band edge emission, with increasing the post-reaction thermal treatment temperature as the tin oxide crystallinity improved. (C) 2007 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.