A citrate method to synthesize 0.94Bi0.5Na0.5TiO3-0.06BaTiO3 nano-powder was studied. The stable gel was obtained by the control of the pH value and temperature of the precursor solution. The BNBT nano-powder was produced after calcining the xerogel at 600°C~800°C. The average grain size of the powder calcined at 700°C for 3 h is 50 nm, and the grain size of the ceramic sintered at 1080°C is 0.7 μm. The sintering temperature used is 100°C lower than the BNBT ceramic prepared by traditional method, but the electrical properties were comparable. In addition, it was found that the ball-milling process has important effect on the morphology of the ceramics and the orientation crystals were eliminated due to the disintegration of agglomerates during milling.