An improved combinatorial hydrate formation promoter was used for hydrate-based carbon dioxide (CO2) capture from simulated flue gas, which consists of cyclopentane (CP), tetra-n-butyl ammonium bromide (TBAB), and glucoamylase. The effects of different glucoamylase concentrations (w(glu) = 0.0, 3.0, 5.0, and 10.0 wt %), feed pressures (2.50-4.50 MPa), and reaction temperatures (274.15-278.15 K) were investigated for hydrate formation in the TBAB/CP/glucoamylase system. The kinetics performance of this system was evaluated by reviewing the CO2 recovery (S.Fr.) and separation factor (S.F.), gas uptake, and the apparent rate constant of hydrate formation. The results indicated the TBAB/CP system with 3.0 wt % glucoamylase solution at 2.50 MPa and 276.15 K to be the optimum experimental condition. Compared to the TBAB/CP system, CO2 separation improved by 22.2%, gas uptake increased by 11.5%, and the rate of hydrate formation accelerated by 67.6% with the presence of combinatorial promoter (TBAB/CP/glucoamylase).