Fisher-Tropsch synthesis for the production of hydrocarbon from syngas was investigated on 20% cobalt-based catalysts (20% Co/HSA, 20% Co/Si-MMS), which were prepared by home-made supports with high surface areas such as high surface alumina (HSA) and silica mesopores molecular sieve (Si-MMS). In the gas phase reaction by syngas only, 20% Co/Si-MMS catalyst was shown in higher CO conversion and lower carbon dioxide formation than 20% Co/HSA, whereas the olefin selectivity was higher in 20% Co/HSA than in 20% Co/Si-MMS. In the effect of n-hexane added in syngas, the selectivities of $C_{5+}$ and olefin were increased by comparing the supercritical phase reaction with the gas phase reaction in addition to reduce unexpected methane and carbon dioxide.