Nanocapacitors and nonvolatile ferroelectric random access memories require nanoscale thin film coatings with ferroelectric properties. One dimensional ferroelectric nanofibers are used in ferroelectric memory devices owing to the fact that decrease of the dimensionality of the memory device elements will reduce the addressing and appreciably increase the storage capacity. Novel ZnO/BaO nanocomposite fibers exhibiting ferroelectric properties have been prepared in the form of non-woven mesh by electrospinning the sol derived from the sol-gel route. Thin cylindrical nanofibers of average diameter 100 nm have been obtained and their morphology is confirmed by SEM and AFM images. In the electrospinning process, the effect of the working distance on the fiber morphology was studied and it showed that working distance between 11 and 15 cm can produce fibers without beads and the decrease in working distance in this range increases the fiber diameter. Powder XRD was used to identify the phases and EDX analysis confirmed the presence of ZnO/BaO. Dielectric and non-linear optical properties have also been studied. The dielectric studies showed that ZnO/BaO composite nanofibers undergo a phase transition from ferroelectric to paraelectric at 323 K.