The aim of this study was to prepare polyvinyl borate (PVB)/poly(methyl methacrylate) (PMMA) blend nanofibers by electrospinning process. Polyvinyl borate was synthesized by the condensation reaction of polyvinyl alcohol and boric acid. FTIR analyses showed that boron atoms were found to be integrated into the polymer network. Blending PMMA with PVB decreased the fiber diameter and enhanced the surface roughness of PVB/PMMA blend nanofiber mats. The water wetting property of the nanofiber mats was influenced by the surface roughness. The blend composition with the highest polyvinyl borate content was found to be suitable for thermally stable nanofiber formation.