Cobalt subtitution on NiSi is investigated by using an ab-initio calculation. Firstly, a relaxed NiSi structure is calculated and the calculated lattice parameters are compared with experimentally determined lattice parameters. The calculated values are smaller than the experimental values by about 2%. As the calculation is based on 0 K, and the experimental measurement is performed at room temperature, those values are in good agreement. Next, a Co atom substitutes a Ni and Si site, respectively, to evaluate the preferable site between them. Co prefers Ni site to Si site. The calculated total energy also indicates that the Co substitution to Ni site stabilizes the NiSi structure. Therefore, the thermal stability of NiSi with Co addition can be achieved by the structure stabilization of NiSi by Co substitution into Ni site of NiSi.