Lead lanthanum zirconate titanate (PLZT) (Pb1–xLax)(Zr0.5Ti0.5)1–x/4O3 (x = 0.01–0.13) piezoelectric ceramics and polyvinylidene fluoride (0–3 PLZT/PVDF) composites were prepared by solid-state sintering process and casting process, respectively. The PLZT ceramic structure was investigated by X-ray diffraction, and the ceramics Curie temperature was determined by measuring critical expansion coefficient points. Dielectric and piezoelectric properties for PLZT ceramics and their composites were analyzed. Results show that, with La substitution content from 0.01 to 0.13, tetragonality of the PLZT ceramic decreases and tetragonal phase is gradually transformed into a rhombohedral phase, while Curie temperature drops almost linearly from 356 ℃ to room temperature. Electric properties are influenced by La substitution in the PLZT ceramic. With the increase of La substitution content, the relative dielectric constant and the dielectric loss exhibit an increasing tendency, while the piezoelectric coefficient and the electromechanical coupling coefficient initially increase and then decrease, achieving maximum values of 224 pC/N and 0.5 at x = 0.07, respectively. For the PLZT/PVDF composites, the relative dielectric constant and piezoelectric coefficient gradually increase with the La substitution content. Notably, the piezoelectric coefficient increased from 20 pC/N to 34 pC/N, which can be attributed to polarization enhancement for the PLZT ceramic phase in composite.