Boron doped PVA/Zr-Al acetate nanofibers were prepared by electrospinning using PVA as a precursor. The effect of calcination temperature on morphology and crystal structure was investigated at 250, 500, and $800^{circ}C$. The study also establishes the effect of boron doping on the morphology of PVA/Zr-Al acetate nanofibers at various calcination temperatures. The measurements showed that the conductivity, pH, viscosity and the surface tension of the hybrid polymer solutions have increased with boron doping. In addition, the fibers were characterized by FTIR, DSC, XPS, XRD and SEM techniques. The addition of boron did not only increase the thermal stability of the fibers, but also increased the average fiber diameters, which gave stronger fibers. The DSC results indicated that the melting temperature (Tm) of the fibers was increased from 256 to $270^{circ}C$ with the addition of boron. XRD peak patterns showed that after further heat treatment at $800^{circ}C$, zirconia exists in two phases of tetragonal and monoclinic modifications. Moreover, alumina does not transform into the ${gamma}-Al_2O_3$ and ${ heta}-Al_2O_3$ phase at $800^{circ}C$. The SEM appearance of the fibers showed that the addition of boron resulted in the formation of crosslinked bright surfaced fibers.