The valence electron topologies of Mg 2 Si thermoelectric materials multi-doped with Al, Zn and Sb have been determined by the Maximum Entropy Method (MEM) using synchrotron X-ray powder diffraction data. In spite of the very low concentrations, expansion was observed in the cubic unit cells of the doped samples. Using pure Mg 2 Si as a reference, charge density difference maps revealed qualitative features on the distributions of the electrons contributed by the doped atoms. The presence of excess electrons shows all doped samples are n-type semiconductors and they are shared among the atomic sites. We evaluated the reliability of the MEM calculated charge density by considering the effect of successively increasing the number of high angle