The silicide formation mechanisms of Co/Hf and Co/Nb bilayer on (100) Si have been investigated. We ob-served that crystallographic orientationso f the 500$^{circ}C$ formed cobalt silcides were different each other with the varying intermediate layers. Epitaxial and non-epitaxial CoSi2 formed simultaneously in Co/Hf/(100Si. While only non-epitaxial CoSi2 formed in Co/Nb/(100) Si. The reason why the crystallographic orientation of CpSi2 is different for those two systems seemed to be relate to the formation and decomposition of stable reaction barriers at high temperature. The stable reaction barrier formed at high temperature could control the uniform diffusion of Co atoms which enables epitaxial growth of CoSi2