The emission of carbon dioxide from the burning of fossil fuels has been identified as a major contributor to green house emissions and subsequent global warming and climate changes. For these reasons, it is necessary to separate and recover CO2 gas. A new process based on gas hydrate crystallization is proposed for the CO2 separation/recovery of the gas mixture. In this study, gas hydrate from CO2/H2 gas mixtures was formed in a semi-batch stirred vessel at a constant pressure and temperature. This mixture is of interest to CO2 separation and recovery in Integrated Coal Gasification (IGCC) plants. The impact of tetrahydrofuran (THF) on hydrate formation from the CO2/H2 was observed. The addition of THF not only reduced the equilibrium formation conditions significantly but also helped ease the formation of hydrates. This study illustrates the concept and provides the basic operations of the separation/recovery of CO2 (pre-combustion capture) from a fuel gas (CO2/H2) mixture.