The superficial chemical environment of the catalyst supports played an important role in heterometallic catalysts preparation. The functions of hydroxy groups on the surface of SiO2 nanosphere was investigated in catalyst preparing and cellulosic biomass conversion to ethylene glycol (EG). The results demonstrated that 15% Ni-20% W/SiO2-OH catalyst was favorable for EG production, with the highest yield of 63.1 and 42.1% from microcrystalline cellulose and hardwood pulp, respectively. The characterization and activity tests suggested that the existence of hydroxy groups could promote the formation of more Ni-W alloys (e.g. NiW, Ni4W) under the same preparing condition, which supplemented and enhanced the incorporation of intrinsic nickel and tungsten catalytic activity, especially for enhancement of retro-aldol condensation reaction. Moreover, the metallic Ni-0 was generated in higher amount when supported on hydroxy-rich SiO2, boosting hydrogenation of the unsaturated intermediates. Finally, the reusability investigation of the catalyst implied that embedded Ni and W in alloys could inhibit leaching of metals in pressurized hot water.