In this study, the CO2 continuous separation experiments were performed in the system of H2 + CO2 + H2O and H2 + CO2 + tetra-n-butylammonium bromide (TBAB) + H2O for TBAB mass fraction, wTBAB of 0 (the water system), 0.05, 0.10, 0.32. The time evolutions of compositions in the gas phase and the hydrate slurry were measured. The H2 compositions in the gas phase for wTBAB of 0, 0.05, and 0.10 reached steady state at 0.87, 0.81, and 0.78 while the CO2 compositions in the hydrate slurry were 1.00, 0.82, 0.79, respectively. It is shown that the experiments succeed in continuously separating CO2 with structure I hydrate and ionic semiclathrate hydrate. On the other hand, the hydrate transportation problem in separation process occurred for wTBAB = 0.32. For wTBAB = 0, the highest values of H2 compositions in the gas phase and CO2 compositions in hydrate slurry were obtained. The concentration of captured CO2 for wTBAB = 0 was comparable to that obtained by multistage process in hydrate-based gas separation or chemical absorption used in the demonstration project of integrated gasification combined cycle.