We report the preparation of sheath-core type fibers made from poly(vinylidene fluoride) (PVDF) and polyarylate (PAR) using melt conjugate spinning to fabricate piezolectric composites. The morphology of this sheath-core fiber was determined through scanning electron microscopy. Subsequently, by the compression molding of the PVDF/PAR sheath-core fiber assembly, we fabricated PVDF/PAR composites exhibiting piezoelectric properties. For enhancing the piezoelectric properties, we increased the concentration of PVDF β-crystalline phase in the PVDF/PAR composite through poling post-treatments. The resulting crystal structure of PVDF was confirmed through infrared spectroscopy and X-ray diffraction. A universal testing machine was employed to measure the tensile properties of the PVDF/PAR composites. Finally, through a hydrothermal growing method, ZnO was coated on the composite surface to enhance the piezoelectric properties, which were subsequently optimized by varying the hydrothermal growing conditions.