This study describes the microstructure, crystal structure, dielectric and piezoelectric behavior of 0.1Pb[Fe1/2Nb1/2]O3-0.9Pb[ZrxTi(1–x)]O3 (x = 0.49-0.55) ceramics synthesized by solid-state reaction. Compositions were sintered at 1180oC for 120 min. Dense and uniform microstructure was seen through microstructural analysis. XRD pattern confirmed the co-existence of tetragonal and rhombohedral perovskite phases in these compositions where 0.51 ≤ x ≤ 0.53. Compositions with 0.51 ≤ x ≤ 0.53 resulted in the optimum values of properties, viz. dielectric constant (ϵrr) of 1150, piezoelectric coefficient (d31) of 95x10–12 C/N, piezoelectric voltage constant (g31) of 70x10–3 mV/N and the coupling factor (kp) value of 0.67. Results indicated that this material composition could be suitable for power harvesting and sensor applications.