Organic inorganic composites with nanostructure could exhibit a diverse range of multi-functional properties. In this study, nafion/silica composite nanofibers were successfully fabricated by using electrospinning technique with nafion coated surface. The tunable wettability of composite nanofiber was controlled by addition of nafion or flame-treatment. The thermal stability of nafion has been improved as it hybridized with silica nanofiber. Interestingly, the hydrophobic behavior still existed after heat-treatment with 500 degrees C for 2 h. The fire resistant property of composite nanofiber has been characterized. The effect of nafion polymer and post treatment on the morphology and wettability of composite nanofiber was evaluated. The mechanism of formation of nafion/silica composite nanofiber during electrospinning process has been proposed. The results of this study improve the understanding of the structure rearrange in organic inorganic sols during high voltage field. (C) 2014 Elsevier Ltd. All rights reserved.