Although the hydrogenolysis of glycerol to 1,2-propanediol is already well developed, the production of the more valuable 1,3-propanediol is still a challenge. To achieve this aim, it is essential to design catalysts showing high selectivity toward the CO cleavage of the secondary hydroxyl group in glycerol. In this work, two different series of Pt/WOx/Al2O3 catalytic systems were studied for the selective hydrogenolysis of glycerol to 1,3-propanediol. The results reveal the necessity to control the tungsten surface density in order to obtain highly dispersed polytungstate species, which are able to produce Bronsted acidity and are involved in the selective formation of 1,3-propanediol. After optimization of the tungsten surface density, the effect of platinum content was also studied. It was found that by improving the interactions between platinum and tungsten oxides, it is possible to increase the selectivity toward 1,3-propanediol. Under optimized conditions, a selectivity toward 1,3-PDO of 51.9% at 53.1% glycerol conversion was obtained. Based on the characterization and activity test results, a reaction mechanism for the Pt-WOx catalytic system in glycerol hydrogenolysis to 1,3-propanediol was also proposed. (C) 2015 Elsevier Inc. All rights reserved.