Magnesium silicide and its solid solutions are among the most attractive materials for thermoelectric generators in the temperature range of 500–800 K. However, while n‐type Mg2(Si,Ge,Sn) materials show excellent thermoelectric performance, the corresponding p‐type solid solutions are still inferior, mainly due to less favorable properties of the valence bands compared to the conduction bands. Here, Li doped Mg2Ge with a thermoelectric figure of merit zT of 0.5 at 700 K is reported, which is four times higher than that of p‐type Mg2Si and double than that of p‐type Mg2Sn. The reason for the excellent properties is an unusual temperature dependence of Seebeck coefficient and electrical conductivity compared to a standard highly doped semiconductor. The properties cannot be captured assuming a rigid band structure but well reproduced assuming two parabolic valence bands with a strong temperature dependent interband separation. According to the analysis, the difference in energy between the two bands decrease with temperature, leading to a band convergence at around 650 K and finally to an inversion of the band positions. The finding of a combination of a light and a heavy band that are non‐rigid with temperature can pave the way for further optimization of p‐type Mg2(Si,Ge,Sn).
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