Selective hydrogenolysis of glycerol to 1,2-propanediol over Cu–MgO catalysts is reported. A series of Cu–MgO catalysts with varying Cu content were prepared by a co-precipitation method. The physico-chemical properties of the catalysts were derived from BET surface area, X-ray diffraction, temperature programmed reduction of hydrogen, temperature programmed desorption of carbon dioxide, X-ray photoelectron spectroscopy, transmission electron microscopy and dissociative N₂O adsorption techniques. The activity results showed that Cu content on MgO has a significant role in glycerol conversion as well as formation of 1,2-propanediol. Well dispersed Cu species and accessible basic sites of MgO are the essential requirements for high glycerol hydrogenolysis activity. 20 wt% of Cu content on MgO is identified as an optimum Cu content. The catalyst is equally active even with crude glycerol and glycerol containing alkali salts as impurity. Different reaction parameters were evaluated and optimized reaction conditions were established.