The performance of supercritical fluid (SCF) as a solvent can be greatly affected by addition of anentrainer to the system. In this study, a constant volume visual method is used to measure the critical point ofCO2+n-butyraldehyde, CO2+ i-butyraldehyde and CO2+alcohol binary systems and CO2+entrainer+trisodiumsalt of tri-(m-sulfonphenyl)phosphine (TPPTS) ternary systems, which provides us good theoretical basis for super-critical extraction and chemical reaction. The relationship between critical point and concentration of the entrainerare discussed. The phase behavior of binary system and that of ternary system are compared. The relationshipbetween the concentration of TPPTS and critical point of binary systems are also discussed.