In this study, it was aimed to prepare polyvinyl borate/polyvinyl alcohol blend nanofibers by electrospinning process. Polyvinyl borate was synthesized by the condensation reaction of polyvinyl alcohol and boric acid. Polyvinyl borate itself was not suitable for electrospinning process. To improve fiber formation capability, polyvinyl borate was blended with polyvinyl alcohol before electrospinning process. A series of nanofibers with various polyvinyl borate concentrations in polyvinyl alcohol were prepared. Homogeneous and highly porous mat containing 100-250 nm diameter nanofibers were obtained by electrospinning process. According to the FTIR results, boron atoms were found to be integrated into the polymer network. There is not any significant effect of polyvinyl borate content on fiber morphologies according to SEM images. The blend composition with the highest polyvinyl borate content was found to be suitable for thermally stable nanofiber formation according to the TGA results. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012