The influences of the substitution of (Zn1/3Nb2/3) group for Ti as well as addition of Fe2O3 and K2CO3 on d33, kp, εr, and tgδ of the Pb[Zr0.46Ti0.54-x(Zn1/3Nb2/3)x]O3 + y mol%Fe2O3+z mol%K2CO3 (PZNPZT) (0 ≤ x ≤ 0.20, 0 ≤ y ≤ 0.10, 0 ≤ z ≤ 0.20) ceramics were investigated. The experimental results demonstrated that when x increases in Pb[Zr0.46Ti0.54-x(Zn1/3Nb2/3)x]O3+0.3 mol%Fe2O3+0.5mol%K2CO3 ceramics, the d33, kp, εr, and tgδ increase and approach to their maximum values, then eventually decrease. XRD analysis revealed that the perovskite structure of the materials transfers from tetragonal phase to rhombohedral phase. The relative dielectric constant (εr) decreases dramatically in the rhombohedral phase area near the MPB; the d33 and εr decrease with the small amount of added Fe2O3 and K2CO3, which also contributes to densification of the PZN-PZT ceramics. The optimized piezoelectric performances through the experiment were obtained as d33=280 pC/N, kp=0.62, εr=900, tgδ=0.003.