X-ray photoelectron spectroscopy, magnetic measurements, and a single-crystal x-ray structure determination at normal pressure have shown that Jahn-Teller active manganese ions in ZnMn2O4 are present in one valence state (III) on the octahedral sites of the spinel structure. The high-pressure behavior of ZnMn2O4 was investigated up to 52 GPa using the energy-dispersive x-ray diffraction technique and synchrotron radiation. The structural first-order phase transition from the body-centered to primitive-tetragonal cell takes place at Pc=23GPa. The high-pressure phase is metastable down to normal pressure. The c/a ratio reduces from 1.62 to 1.10 above Pc and remains nearly pressure independent in the high-pressure phase. The transition is attributed to the changes in electron configuration of the Mn3+ ions. According to the crystal field theory, the eg electron of octahedrally coordinated Mn3+ is either in the d2z orbital or in the dx2−y2. In the first configuration the MnO6octahedron will be elongated and this is the case at normal pressure, while the second configuration gives the flattened octahedron. In the high-pressure phase some proportion of the eg electrons of the Mn3+ ions is moved to the dx2−y2 level, which is revealed as an abrupt fall of observed magnitude of the distortion of the bulk crystal above Pc
