Jahn-Teller distortions are often observed in CuII-containing complex oxides resulting in remarkable changes of physical properties. Tuning the Jahn-Teller distortions with pressure has attracted considerable interest but is less studied in CuII-containing high-entropy oxides (HEOs). We found that pressure can suppress the structural distortions originating from the Jahn-Teller effect of CuO6 octahedra in the rock salt-type (Mg0.2Ni0.2Co0.2Zn0.2Cu0.2)O HEO and significantly modify its electronic properties. Synchrotron x-ray diffraction shows that the structural distortions arising from the Jahn-Teller effect of CuO6 octahedra are progressively suppressed, and the distorted structure evolves into a nearly ideal form under compression. Alternating current impedance and ultraviolet-visible absorption measurements reveal a dramatic resistance drop by more than three orders of magnitude and an obvious bandgap decrease in ∼0.1 eV, respectively, accompanied by the pressure-induced suppression of structural distortions. Our study presents a promising route for tuning the structural distortions and the electronic structures of CuII-containing HEOs for optimizing materials functionalities.

High-entropy oxides (HEOx) are multicomponent (≥5) complex oxides that possess material properties and functions unexpected from their constituent simple oxides. Previous studies demonstrated that a cation-doped HEOx, MgCoNiCuZnO5, shows good catalytic activity, excellent ionic conductivity, and high energy storage. The structural and mechanical stabilities of materials are pivotal to their applications. However, how temperature and pressure influence the structural stability of cation-doped HEOx and how doping affects the mechanical properties are yet to be understood. In this work, we investigated the structural stabilities of undoped and Li/Mn-doped MgCoNiCuZnO5 in heating or under compression using in situ synchrotron X-ray diffraction (XRD), and determined their elastic moduli using high-pressure XRD. Our results show that the HEOx compounds are structurally stable at temperatures up to ∼450 °C or at pressures up to ∼50 GPa, and that Li/Mn doping makes the HEOx more compressible. Our molecular static (MS) calculations predicted that the formation reaction of a HEOx is endothermic, consistent with the fact that a single-phase HEOx can only be produced at high temperatures. The MS calculations also revealed that the observed doping-induced elastic softening stems from the introduction of the Li-O/Mn-O ionic bonds in the HEOx compound, which are weaker than other cation-oxygen ionic bonds in the undoped HEOx. These findings will be indispensable to engineer HEOx materials for use in ion batteries, catalysis, and other fields.