A novel organic/inorganic hybrid copolymer poly[styrene-co-3-(trimethoxysilyl)propyl-methacrylate] [P(St-co-TMSPMA)] (denoted as PST) was successfully prepared from styrene and TMSPMA by free-radical polymerization. These composite fiber mats of PST were fabricated via a typical electrospinning process using a single solvent system. As shown in the SEM, the PST composite nanofibers have a smooth and uniform surface and the average diameter is about 0.2 +/- 0.04 mu m. After the methoxysilyl groups (Si-O-CH3) were hydrolyzed toward silanol groups (Si-OH), the nanofibrous mats exhibited remarkable solvent and temperature resistance. On account of good chemical and thermal stability, this hybrid mats can provide a useful platform for developing functionalized mat systems. (C) 2012 Elsevier B.V. All rights reserved.