We present an experimental and computational investigation of the structural properties of the MgCu2O3 compound in ambient conditions as well as at high pressure. The MgCu2O3 compound was synthesized by solid-state reaction and characterized by x-ray diffraction (XRD) using synchrotron source. Rietveld refinement of ambient XRD data shows the orthorhombic crystal structure (isostructural with CaCu2O3, g u¨ ggenite α-type) consisting of edge-sharing octahedra of MgO6 and CuO6, later of these showing distortion due to Jahn-Teller effect which reduces with pressure. The bond angles of Cu–O–Cu along the a-axis and in the plane perpendicular to the a-axis were also investigated. High-pressure XRD data show that the compound is stable up to 20 GPa. The bulk modulus of the MgCu2O3 compound is 110 ± 5 GPa. The compound's mechanical properties are also investigated and discussed.