The thermal properties of clathrate hydrate formed from TBAB+H2O and TBAB+CO2+H2O systems were investigated with differential thermal analysis (DTA) device in the present work. The initial conditions were: 4.43~9.01 wt% for TBAB concentration and 0.5~2.5 MPa for CO2 pressure. The results for TBAB+H2O system show that although two types of TBAB hydrates formed, type A TBAB hydrate is converted into type B TBAB hydrate in the end owing to its instability. In the presence of TBAB, the three-phase equilibrium pressure of CO2 hydrate is reduced by approximately 70-90% depending on the concentration of TBAB aqueous solution. Moreover, higher concentration of TBAB results in lower formation pressure. Compared with THF, TBAB exhibits similar ability of shifting the equilibrium line of CO2 hydrate to lower pressure, but the TBAB+CO2+H2O system displays stronger dependency on temperature.