W or Mo directly deposited on Si cold substrate by electron-beam gun at a base pressure of 10-6 torr is not able to form silicide even annealed at 900 °C in either N2 or H2 ambient. We present an easy way that Mo and W silicides can be formed on the same depositing and annealing conditions with the help of an intervened layer of cobalt or its alloy. Investigation was made on various metallizations of Mo (or W)/Co/Si, W/Co-Mo/Si, and Co/Mo/Si in normal flowingnitrogen or in H2 ambient at various temperatures. In the systems of Mo (or W)/Co/Si and W/Co-Mo/Si, the overlying Mo (or W) can be transformed into silicide at 900 °C, while in the Co/Mo/Si system, where stable Co-Mo compounds are formed in advance, no silicide can be formed. Why silicide is formed in preference to metal oxide in N2 environment at higher temperature is based on Ellingham diagram.