Biodiesel, derived from vegetable oil via hydrotreating, is becoming a promising alternative energy. Novel Ni-Mo-W/gamma-Al2O3-ZSM-5 catalysts were developed and firstly applied in palm oil hydrogenation process. The catalysts were prepared by extrusion method and characterized by XRD, SEM, TEM, BET, NH3-TPD, and H-2-TPR The influences of acidity on the activity, selectivity, and stability of catalysts were systematically studied. The mechanisms of deoxygenation and isomerization were discussed. The catalyst Ni-Mo-W (5 wt.%-5 wt.%-15 wt.%)/gamma-Al2O3-ZSM-5 (85 wt.% 15 wt.%) was confirmed as the optimum one. Finally, the key reaction parameters such as reaction temperature, pressure, liquid hourly space velocity and H-2/oil volume ratio were optimized. The hydrogenation reaction path of palm oil was also proposed. (C) 2015 Elsevier B.V. All rights reserved.