The selective hydrogenolysis of bioglycerol to 1,2-propanediol was investigated over a series of Ce-promoted Cu/Mg catalysts, namely, Cu/Mg (1/9), Cu/Ce/Mg (1/1/5), Cu/Ce/Mg (1/3/5), and Cu/Ce/Mg (1/5/5) prepared by a coprecipitation method. The physicochemical properties of the synthesized catalysts were analyzed by XRD, Raman, BET, BJH, XPS, NH3- and CO2-TPD, and H2-TPR techniques. The XRD and BET surface area results indicated that addition of Ce to Cu/Mg sample remarkably inhibits the crystal growth of CuO and improves the specific surface area. More number of oxygen vacancy defects were found in the Cu/Ce3/Mg sample, as evidenced from Raman studies. The reducible nature of the Cu/Mg sample was significantly enhanced after the Ce-incorporation. The NH3- and CO2-TPD results show that the acid-base properties of the Ce-promoted Cu/Mg samples are highly dependent on the Ce-loading. Among the synthesized samples, the Cu/Ce3/Mg sample exhibited higher concentration and superior strength of acidic sites. The achieved activity order of various catalysts for glycerol hydrogenolysis is Cu/Mg