The 0.94Bi0.5(Na1-xLix)0.5TiO3-0.06BaTiO3 (x=0.06%,0.10%,0.15%,0.20%) binary leadfree piezoelectric ceramics are prepared by the conventional solidphase sintering method. The influences of the different Li2O contents on the phase structure, microstructure, piezoelectric and dielectric properties of the BNTbased ceramics are studied systematically. The results show that the BNBT6 ceramics doped with different contents of Li2O have a uniformly distributed grain size, high density and exhibit the morphotropic phase boundary structure with the coexistence of trigonaltetragonal system. The different contents of Li2O does not affect the phase structure of the ceramics , but the sintering properties and electrical properties of 0.94Bi0.5(Na1-xLix)0.5TiO3-0.06BaTiO3 based ceramics are tightly related to the Li2O contents. Whenx=0.15%, the BNBT6 ceramics samples show superior performance with high relative density of 98%, high piezoelectric constant of d33=130 pC/N, high dielectric constant of εr =971, high mechanical quality factor ofQm=367, and lower dissipation factor of tan δ=2.0% at a frequency of 1 kHz.