Abstract The (1 − x)Na1/2Bi1/2TiO3–x(Na1/4Bi3/4)(Mg1/4Ti3/4)O3[abbreviated as (1 − x)NBT–xNBMT] lead-free piezoelectric ceramics were prepared by conventional ceramic processing. The results of the XRD and SEM suggested that NBMT addition resulted in insignificant influence on crystal structure within the studied content. Up to 12% mol NBMT can dissolve into the lattice of NBT to form a solid solution with a single perovskite structure. However an obvious change in microstructure took place. With increasing NBMT content, the temperature for a transition from antiferroelectric phase to paraelectric phases keeps almost same value, and the temperature for a ferroelectric to antiferroelectric phase transition is clearly reduced, which leads to the broader antiferroelectric phase zone. The piezoelectric properties of the ceramics are sensitive to the compositions, and the composition with x = 0.06 exhibits highest piezoelectric properties of d33 = 98pC/N and kp = 0.201.