In this sudy, it was aimed to synthesize polyvinyl borate and to prepare its nanofiber, by electrospinning process. Polyvinyl borate (PVB) was synthesized by the condensation reaction of polyvinyl alcohol and boric acid. To improve fiber formation capability, polyvinyl borate was blended with polyvinyl alcohol (PVA) and poly (methyl methacrylate) (PMMA), separately, before the electrospinning process. A series of nanofibers with various polyvinyl borate concentrations in polyvinyl alcohol and poly methyl methacrylate were prepared. Homogeneous and highly porous mats containing 100–250 nm diameter nanofibers were obtained from PVB/PVA blend solution by the 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 of PVB/PVA nanofiber mats. The blend compositions with the highest polyvinyl borate content was found to be suitable for thermally stable nanofiber formation according to the TGA results. In addition; according to SEM images, blending PMMA with PVB decreased the fiber diameter from 218 nm to 93 nm and resulted in appearing the bead structures along the fibers, which increased the surface roughness of PVB/PMMA blend nanofiber mats. The water wetting property of PVB/PMMA blend nanofiber mats was influenced by the surface roughness. The contact angle increased with increasing the PVB content of PVB/PMMA blend nanofibers.