The precalcined and calcined silica supported cobalt catalysts at 15, 20, and 25%Co were investigated by X-ray Absorption Spectroscopy (XAS) including the X-ray absorption near edge structure (XANES) and the extended X-ray absorption fine structure (EXAFS). The results showed the phase of Co(NO3)2.6H2O in all precalcined catalysts, which corresponded to the XRD measurement. When increasing the amount of cobalt in the precalcined catalysts, there was the presence of ordered Co(NO3)2.6H2O phase. After calcination in Ar at 600°C for 6 h, the Co3O4phase was presented in all calcined catalysts. For the catalytic performance testing, the selected 20%Co/Aerosil_wi_calcined catalyst was reduced at 450°C in H2and operated at 190°C with a total pressure of 10 bar and H2/CO flow rate of 20:10 ml/min for Fischer-Tropsch synthesis. After reaction testing, the used 20%Co/Aerosil_wi catalyst showed the main phase of Co3O4. The result showed high methane selectivity at the beginning of reaction. By increasing of reaction time, the methane selectivity tended to decrease, whereas the C2-C4and C5+selectivity was increased.