The quarternary system ceramics 0.5[yPb(Zn1/3Nb2/3)O3-(1-y)Pb(Ni1/3Nb2/3)O3]-0.5[xPbTiO3-(1-x)PbZrO3](PZN-PNN-PT-PZ) was fabricated by the columbite precursor method to obtain a stabilized perovskite structure and by conventional method to evaluate the efficiency of the former methd. Dielectric and piezoelectric properties were investigated and the stability of the perovskite phase was studied as a function of PZN and PT contents and firing temperature. In the samples prepared by the columbite precursor method, the pyrochlore phase, which is detrimental to both the dielectric and piezoelectric properties, was not observed in the absence of PZN, and electric properties were improved even when fabricated at low temperature. By adding PZN, some pyrochlore phase appeared and the morphotropic phase boundary of the samples shifted to more Zr-rich composition. The temperature dependence of piezoelectric constant decreased with the addition of PZN, due to the rising of the Curie point.