The formation of hydroquinone (HQ) clathrate and the guest behaviors of binary (CH4 + CO2) gas mixtures were investigated by focusing on an application to separate CO2 from landfill gases. Spectroscopic measurements show that at two experimental pressures of 20 and 40 bar, CO2 molecules are preferentially captured in HQ clathrates regardless of the gas composition. In addition, preferential occupation by CO2 is observed more significantly when the formation pressure and the CH4 concentration are lower. Because the preferential occupation of CO2 is found with binary (CH4 + CO2) gas mixtures regardless of the composition of the feed gas, a clathrate-based process can be applied to CO2 separation or concentration from landfill gases or (CH4 + CO2) mixed gases.