We use X-ray absorption spectroscopy to study the electronic structure of Bi and Si-doped double CaMnO3 thermoelectric materials. From the O K-edge spectra can be seen 2% doped sample its Mn3d-O2p hybrid orbitals strongest from Mn L2 ,3-edge spectra can be seen the proportion of Mn +4 Mn +3 is also 2% doped the highest sample found from Ca L2 ,3-edge spectra of Ca doping in all 3d orbitals are empty decline, found several empty orbitals of all doping Mn 4p from Mn K-edge spectrum are added, the result shows that the conductive layer from the spectrum (MnO2 layer) due to the carrier concentration and the Si-doped Bi after increasing trend. Thermoelectric properties of nature-related measurements showed a 2% doped sample resistance, thermal conductivity and thermal electricity are the lowest, and the highest quality coefficient. Si-doped Bi and we will cause changes in the electronic structure and its impact on the thermoelectric properties of the mechanism for a more in-depth discussion.