In this study, both boron-doped and -undoped poly(vinyl alcohol)/Calixarene fibers were prepared by using an electrospinning technique. Obtained fibers were characterized by FT-IR, DSC, and SEM techniques. The DSC results show that the degradation of the boron-doped fibers started at much higher temperatures. This result indicates the addition of boron increased the thermal stability of the fibers. SEM pictures show that both of the fiber samples are nonbeaded with diameters ranging from 0.5 to 1 mu m. The fiber diameters are not homogeneous and uniformly distributed for boron-undoped samples.