Supported Cu–Cr catalysts were prepared by a non-alkoxide sol–gel route, and characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), H2-temperature programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS) measurement. Their structures were significantly tuned by the Cu–Cr molar ratio. CuCr2O4, CuCr2O4–CuO and CuCr2O4–Cr2O3 structures were confirmed in CuCr(0.5), CuCr(4) and CuCr(0.25) catalysts, respectively. A direct interaction between CuCr2O4 and CuO or Cr2O3 in CuCr(4) and CuCr(0.25) catalyst was observed by the H2-TPR and XPS results. The catalytic performance of Cu–Cr catalysts with various structures was examined by hydrogenolysis reaction of high concentrated glycerol. Under mild conditions (2.0 MPa and 130 °C) and high concentration (100 wt%), the maximum conversion (52%) was obtained over the CuCr(0.5) catalyst, while the CuCr(4) catalyst gave the highest selectivity of 1,2-PD (up to 100%). This finding will result in the production of less waste water and lower energy consumption in the following separation steps during glycerol hydrogenolysis.