xPb(Ni1/3Nb2/3)O3-(1-x)Pb(Zr,Ti)O3 (x = 0.12, 0.24, 0.36, 0.42, 0.55 and 0.64) ceramics were prepared using conventional solid-state reaction. The morphotropic phase boundary (MPB) composition region, sintering characteristics and performance parameters of ceramic samples with different PNN compositions were studied. The phase structure, microstructure and electrical properties were characterized in detail. The results show that the Curie temperature (TC) of PNN-PZT ceramics decreases from 324 °C to 44 °C while the piezoelectric coefficient (d33) changes from 43 pC/N to 1170 pC/N with PNN content from 0.12 to 0.64. Interesting phenomena were observed, which can provide useful information for practical applications of PNN-PZT ceramics.