We determined phase relations in MgCr2O4 at 12–28 GPa and 1000–1600 °C using a multi-anvil apparatus. At 12–15 GPa, spinel-type MgCr2O4 (magnesiochromite) first decomposes into a mixture of new Mg2Cr2O5 phase + corundum-type Cr2O3 at 1100–1600 °C, but it dissociates first into MgO periclase + corundum-type Cr2O3 at l000 °C. At about 17–19 GPa, the mixture of Mg2Cr2O5 phase + corundum-type Cr2O3 transforms to a single MgCr2O4 phase. Structure refinements using synchrotron X-ray powder diffraction data indicated that the high-pressure MgCr2O4 phase has a CaTi2O4-type structure (Cmcm), and that the basic structure of the Mg2Cr2O5 phase is the same as that of recently found modified ludwigite-type Mg2Al2O5 and Fe2Cr2O5 (Pbam). The phase relations in this study may suggest that natural chromitites in the Luobusa ophiolite regarded as the deep-mantle origin were derived from the mantle shallower than the depths corresponding to pressure of 12–15 GPa because of absence of the assemblage of (Mg,Fe)2Cr2O5 + Cr2O3 in the chromitites.