Abstract (1 − x )Bi 0.5 Na 0.5 TiO 3 – x (Ba 0.85 Ca 0.15 )(Ti 0.90 Zr 0.10 )O 3 [(1 − x )BNT– x BCTZ] lead-free piezoelectric ceramics were prepared by a conventional solid reaction method. A stable solid solution is well formed between BNT and BCTZ. The ɛ r increases, and the T m , T d , and the density slightly decrease with increasing BCTZ content. Moreover, the d 33 value of (1 − x )BNT– x BCTZ ceramics with x = 0.06 demonstrates a temperature independence and a poling electric field dependence. (1 − x )BNT– x BCTZ ceramics with x = 0.06 exhibit an optimum electrical behavior: d 33 ∼ 158 pC/N, k p ∼ 31.2%, and ɛ r ∼ 1165, which is much better than that of pure BNT ceramic. As a result, (1 − x )BNT– x BCTZ ceramics are a promising candidate material for the piezoelectric device.