Unsupported NiMo sulfide catalysts modified by tungsten were prepared by a mechanical activation method. They were characterized by XRD, XPS, SEM, TEM and BET specific surface area measurements. The effect of tungsten promoter on the structure and catalytic performance was also discussed. The present work suggested that the addition of tungsten could greatly enhance the hydrodeoxygenation (HDO) activity, and promote the direct deoxygenation (DDO) pathway. Moreover, the addition content affects the mount of active NiMo(W)S phase, resulting in various functions. (C) 2014 Elsevier B.V. All rights reserved.