In this study, boron doped and undoped poly(vinyl) alcohol/zirconium-barium acetate (PVA/Zr-Ba) nanofibers were prepared using an electrospinning technique then calcinated at three different temperatures; 250 degrees C, 500 degrees C, 800 degrees C for 2 h. The originality of this study is the addition of boron to metal acetates. The fibers were characterized by FT-IR, DSC, XRD and SEM. The addition of boron did not only increase the thermal stability of the fibers, but also increased their diameters, which gave stronger fibers. The FT-IR spectra of the fibers were in good accordance with literature data. The DSC results indicate that the glass transition (Tg) and melting temperatures (Tm) showed a change with the addition of boron. Also, boron doped fibers were observed to degrade at higher temperatures. XRD analyses showed that after further heat treatment at 800 degrees C, zirconia exists in two phases of tetragonal and monoclinic modifications. The systematic evolution of morphological features in the spun and the processed fibers were studied by scanning electron microscopy. The SEM appearance of the fibers showed that the addition of boron resulted in the formation of cross linked bright surfaced fibers.