Abstract: Using the highly accurate G4 method, we computed the thermodynamic data of 1287 possible reaction products under a wide range of reaction conditions in the Fischer-Tropcsh synthesis (FTS) process. These accurate thermodynamic data provide basic thermodynamic quantities for the actual chemical engineering process and are useful in analyzing product distribution because FTS demonstrates many features of an equilibrium-controlled system. Our results show that the number of thermodynamically allowed products to increase when lowering temperature, raising pressure, and raising H₂/CO ratio. At low temperature, high pressure and high H₂/CO ratio, many products are thermodynamically allowed and the selectivity of product has to be controlled by kinetic factors. On the other hand, high selectivity of lighter products can be realized in thermodynamics by raising temperature and lowering pressure. We found that the equilibrium product yield will reach a maximum and remain unchanged when lowering temperature, raising pressure, and raising H₂/CO ratio to some limits, implying that optimizing reaction conditions has no effect on equilibrium product yields beyond these limits. The thermodynamic analysis is also useful in designing and evaluating FTS reaction mechanisms. We found that reaction pathways through formaldehyde should be discarded because of its extremely low equilibrium yield. Recently, in the FTS process using metal-oxide-zeolite catalysts for the highly selective production of C₂-C₄ olefins and aromatic hydrocarbons, there are several guesses on the possible reaction intermediates entering the zeolite channel. Our results show that ketene, methanol, and dimethyl ether are three possible reaction intermediates.