We determined the chemical and isotopic compositions of the liquid CO2 found on Yonaguni IV knoll hydrothermal site, as well as those in hydrothermal fluid venting from the surrounding chimneys. The δ13C of both CO2 and CH4 in the liquid CO2 almost coincide with those in the hydrothermal fluid, suggesting that the liquid CO2 must be derived from the hydrothermal fluid. While showing homogeneous δ13C, the hydrothermal fluids exhibit wide variation in gas contents. Active phase separation must be taking place within the conduits. Besides, H2-depletion in the liquid CO2 suggests formation of solid CO2-hydrate must also precede the venting of liquid CO2. In conclusion, liquid CO2 must be produced through following subseafloor processes: phase separation of hydrothermal fluid due to boiling, formation of solid CO2-hydrate due to cooling of vapor phase, and melting of the solid CO2-hydrate to liquid CO2 due to a temperature increase within the sedimentary layer.