Pb(Zr0.48Ti0.52)O3 (PZT) micro/nano-fibers and mats were synthesized from alkoxides using electrostatic deposition. The PZT micro/nano-fibers precursor, a mixture of zirconium npropoxide, titanium isopropoxide, and lead 2-ethylhexanoate, was deposited under the following conditions: tip-screen distance=15cm, voltage drop between tip and screen of 15kV. The deposited fibers and mats samples were sintered for half an hour at 400, 500, 600, 700, and 800°C, respectively. Sintered mats were characterized using x-ray diffraction (XRD), sintered fibers were characterized using optical microscope, scanning electron microscopes (SEM), Raman microscope, and scanning probe microscope (SPM). SEM revealed that micro/nano-fibers have diameters varying from a fraction of a micron to around 10 micrometer. XRD and Raman spectra indicated that the precursors begin to transform into intermediate phase Pb2Ti2O6 at 400°C, whose transformation into the perovskite phase starts at 600°C and ends at 800°C. Scanning probes microscope (SPM), operated in voltage-modulated dynamic contact mode, revealed the spontaneous polarization domains, with diameters ranging from 0.1 to 0.5 micron, in microfibers, confirming their piezoelectricity.