In this paper, (Pb0.9Sr0.1)(Zn1/3Nb2/3)(0.06+x)(Ni1/3Nb2/3)0.16(Zr0.52Ti0.48)(0.78-x)O3 (PSZN-PSNN-PSZT, x = 0, 0.02, 0.04, 0.06, 0.08) piezoelectric ceramics were prepared by traditional solid-state reaction method. The samples were studied on microstructure, phase structure, electrical properties and dielectric relaxation. All as-prepared PSZN-PSNN-PSZT ceramics present single phase of perovskite structure. Experimental results show that the variation trend of the R phase percentage content is consistent with the trend of d33. Also, increasing PSZN content will inhibit the growth of sample grains. The temperature-dependent of dielectric performance testing results present that all the samples possess obvious relaxation behavior. The best overall performance of the samples are obtained at x = 0.06, where its d33 = 920pC/N, kp = 0.71, Pr = 24.54 μC cm−2, γ = 1.98, ε
r = 6856, tanδ = 3.3%, Tc = 133 ℃. The PSZN-PSNN-PSZT ceramics are potential candidate materials due to its simple preparation process, the high dielectric and piezoelectric properties.