A unique growth mechanism of nickel silicide (NiSi) nanowires (NWs) was thermodynamically investigated. The reaction between Ni and Si primarily determines NiSi phases according to the deposition condition. Optimum growth conditions were found at 375 °C leading long and high-density NiSi NWs. The ignition of NiSi NWs is determined by the grain size due to the nucleation limited silicide reaction. A successive Ni diffusion through a silicide layer was traced from a NW grown sample. Otherwise Ni-rich or Si-rich phase induces a film type growth. This work demonstrates specific existence of NiSi NW growth.