AbstractPolycrystalline skutterudite Ba0.4Co4Sb11.7Te0.3 with a bcc crystal structure was prepared by the High-Pressure and High-Temperature (HPHT) method. The study explored a chemical method for introducing Ba atoms into the voids of CoSb3 to optimize the thermoelectric figure of merit ZT in the system of Ba0.4Co4Sb11.7Te0.3. The samples were characterized by X-ray diffraction, electron microprobe analysis, and thermoelectric properties measurement. The electrical resistivity, Seebeck coefficients and thermal conductivities of the samples were measured in the temperature range of 300–743 K. The power factor and the figure of merit, ZT, of the samples all increased with the increasing temperature. A dimensionless thermoelectric figure of merit of 0.87 at 743 K was achieved for n-type Ba0.4Co4Sb11.7Te0.3 at last. The results indicated Ba-filled CoSb3 prepared by HPHT method is an effective method to greatly enhance the thermoelectric properties of skutterudite compounds.