It is the important way to improve thermoelectric properties of skutterudite materials by doping with rare earth elements. The mechanisms of improving properties of bulk RExCo4Sb12materials prepared by mechanical alloy and spark plasma sintering (MA-SPS) at 650°C were investigated by analyzing the composition, microstructure and atomic occupying locations. According the results it can be considered that the mechanism to improve the thermoelectric properties of rare earth elements is that rare earth element Ce in the samples mainly plays the doping role in reducing the resistivity of the sample and improving the conductivity, so that it makes the figure of merit ZT of samples increase significantly.