(1-x)(0.64PNN-0.36PT)-x(0.91PZN-0.09PT) ferroelectric ceramics with different x were synthesized by the columbite precursor method. The phase structure and piezoelectric properties were investigated. XRD profiles implied that with the increasing of x, samples could no longer maintain the pure perovskite phase. All the compositions were found to lie within the region of the morphotropic phase boundaries (MPBs) with different contents of rhombohedral and tetragonal phases. The piezoelectric coefficients for compositions with x £ 0.30 were obviously better than those for the rest ones and the composition with x = 0.15 exhibited the largest value of d33 among all the samples. The relationship between the structure and the piezoelectric properties was discussed.