Organic-inorganic hybrid materials were prepared starting from tetraethoxysilane and alpha- or alpha,omega-triethoxysilane terminated poly(F-caprolactone) (PCL-Si) using the sol-gel process. In all cases the formation of nanocomposites with a high level of interpenetration between organic and inorganic phases was noted. Poly(methyl methacrylate) slabs were dip-coated with PCL-Si/silica hybrids and a very strong increase of the flame resistance (also after UV irradiation) was noted for all coating compositions without marked differences with respect to hybrid compositions. This behavior was attributed to a preferential segregation of silica onto the outer surface, as evidenced by XPS analysis. (C) 2003 Elsevier Science Ltd. All rights reserved.