The highly strained interfacial structure and reaction of Co on Si(111) in the initial growth stage was studied by in-situ surface x-ray scattering. Co was deposited on Si(111) – (7×7) reconstruction by electron beam evaporation in ultra high vacuum. Our study reveals that the interfacial layer, formed by the reaction of Co with Si in the initial growth stage at room temperature, is a silicide layer with stoichiometry of Co2Si. The interfacial silicide layer is a commensurate phase of pseudohexagonal Co2Si, which shows a significant local atomic displacements imposed by Si substrate. The intensity oscillations at the anti-Bragg position with Co coverage show that a layer-by-layer consumption of silicon substrate occurs for the first 15 monolayers (ML) of Co deposited.