This paper reports the effect of lanthanum addition on the structural and electrical properties of (Pb1-xLax)(Zr0.65Ti0.35)O3 (PLZT x/65/35, x = 8%,10%,12%,15%) ceramics near the morphotropic phase boundary. Studies were conducted on the PLZT x/65/35 ceramics synthesized via a combinatorial approach of high-energy ball milling (mechanical activation method) followed by Cold Isostatic Pressing (CIP). Due to the application of CIP, PLZT ceramics exhibited improved density and a closely packed microstructure. The SEM analysis showed that PLZT x/65/35 ceramics exhibited an increase in grain size with higher concentrations of La3+ ions. Room temperature X-ray diffraction results revealed the formation of perovskite PLZT phase. The investigation on temperature-dependent dielectric, ferroelectric properties of PLZT x/65/35 ceramics provided experimental confirmation of structures cited in XRD analysis. Among all the compositions, PLZT 8/65/35 samples showed a well saturated, uniform P–E hysteresis loop with a high remanent polarization (Pr). Poled PLZT 8/65/35 samples displayed electric field induced large strains with limited hysteresis. Piezoelectric charge coefficients (d33), electromechanical coupling factors (kp, k33, k31) were determined for poled PLZT x/65/35 ceramics and it was found that PLZT 8/65/35 ceramics reveal properties superior to other compositions. Furthermore, the unipolar strain, Pr, d33, kp, k33, k31 values of PLZT 8/65/35 composition exceeded the previously reported ones for the same composition prepared via sol-gel synthesis technique.