AbstractSolid oxide fuel cells (SOFCs) are paving the way to clean energy conversion, relying on efficient oxygen‐ion conductors with high ionic conductivity coupled with a negligible electronic contribution. Doped rare earth aluminates are promising candidates for SOFC electrolytes due to their high ionic conductivity. However, they often suffer from p‐type electronic conductivity at operating temperatures above 500 °C under oxidizing conditions caused by the incorporation of oxygen into the lattice. High entropy materials are a new class of materials conceptualized to be stable at higher temperatures due to their high configurational entropy. Introducing this concept to rare earth aluminates can be a promising approach to stabilize the lattice by shifting the stoichiometric point of the oxides to higher oxygen activities, and thereby, reducing the p‐type electronic conductivity in the relevant oxygen partial pressure range. In this study, the high entropy oxide (Gd,La,Nd,Pr,Sm)AlO₃ is synthesized and doped with Ca. The Ca‐doped (Gd,La,Nd,Pr,Sm)AlO₃ compounds exhibit a higher ionic conductivity than most of the corresponding Ca‐doped rare earth aluminates accompanied by a reduction of the p‐type electronic conductivity contribution typically observed under oxidizing conditions. In light of these findings, this study introduces high entropy aluminates as a promising candidate for SOFC electrolytes.