Fluoroalkyl end-capped trimethoxyvinylsilane oligomers, trimethoxyvinylsilane-N,N-dimethylacryl-amide cooligomers, and trimethoxyvinylsilane-acryloyl-morpholine cooligomers were polymerized with hydrolysis and condensation between tetraethoxysilane (TEOS) and trimethoxysilyl segments in oligomers to afford homogeneous fluoroalkyl end-capped oligomers/silica gel polymer hybrids under mild conditions. Similarly, fluoroalkyl end-capped N,N-dimethylacrylamide oligomers and acryloylmorpholine oligomers reacted with TEOS under mild conditions to afford the fluorinated oligomers/silica gel polymer hybrids. The formation of these fluorinated oligomers/silica gel polymer hybrids is due to the homogeneous incorporation of fluoroalkyl end-capped oligomers into the silica gel networks through the intermolecular hydrogen bonding interaction between the residual silanol groups in silica gels and amido groups of fluorinated oligomers. We have also succeeded in preparing new fluorinated polymer hybrids by the use of fluoroalkyl end-capped N,N-dimethylacrylamide co-oligomer-containing silsesquioxane segments. Thermal stability of a variety of fluoroalkyl end-capped oligomers/silica gel polymer hybrids thus obtained was found to increase significantly compared to those of the parent fluoroalkyl end-capped oligomers. In addition, in these fluorinated oligomers/silica gel polymer hybrids, their sol solutions are applicable to the surface modification of glass to exhibit not only a strong oleophobicity imparted by fluorine but also a good hydrophilicity on the glass surface. Therefore, these fluorinated oligomers/silica gel polymer hybrids are suggested to have high potential for new functional materials through their unique properties imparted by not only fluorine but also by the hybrid counterparts. (c) 2005 Wiley Periodicals, Inc.