PZT-Poly(vinylidene fluoride) composites were prepared by hot-pressing method. Before addition, PZT particles were firstly modified with two different coupling agents. The micromorphology, microstructure, dielectric properties, and piezoelectric properties of the composites were characterized and investigated. Results indicated that PZT particles were homogeneously dispersed in the PVDF matrix by the addition of coupling agents. The electric properties of PZT-PVDF composites with NDZ-101 were the best. Especially when the volume ratio of the titanate coupling agent NDZ-101 was 1%, the piezoelectric strain constant d33 of PZT-PVDF composites reached maximum value 19.23pC/N; its relative dielectric constant εr was 67.45; at the same time its dielectric loss tanδ was 0.0766.