Piezoelectric barium zirconate-titanate ceramic nanofibers were prepared by combination of Sol-Gel processing and electrospinning technique. The average diameter of barium zirconate-titanate ceramic nanofibers is nearly 200 nm. The x-ray diffraction pattern of the fibers showed that their crystalline structures displayed tetragonal perovskite structures. Interdigitated electrodes were sprayed on an epoxy resin substrate. BaTi0.9Zr0.1O3 nanofibers were then aligned on the interdigitated electrodes and covered with the solution of epoxy resin, so as to obtain Piezoelectric Fiber/polymer Composites. The periodic output voltages with maximum value of 0.26V were obtained under harmonic excitation, by using a finger to apply a dynamic load on the top of the composites.