Dense lead-free binary system piezoelectric ceramics (1 -x)[Bi-0.5(Na0.7K0.25Li0.05)(0.5)]TiO3-xBa(Ti0.95Zr0.05)O-3 (BNKLT-BZT) were prepared by a two-step sintering process. A phase transition from rhombohedral to tetragonal was observed with increasing BZT fraction in the range x = 0.06-0.1 and the morphotropic phase boundary (MPB) between rhombohedral and tetragonal appears in this range. Ceramics containing 10 mol% BZT with tetragonal phase near the MPB region has the maximum piezoelectric constant d(33)(151pC/N).