Supercritical fluid extraction (SFE) has become an important and useful technique to prepare samples before analysis. The use of supercritical CO2 yields a rapid and quantitative extraction of phthalate plasticizers added to poly(vinyl chloride) (PVC) products. One of them is the plasticized PVC which is a material commonly used in toy manufacturing and other industries. SFE conditions affecting the extraction efficiency have been studied and optimized when pure CO2 is used. Firstly, the influence of the sample particle size in the extraction process has been studied. A fast and quantitative extraction is obtained when the surface/volume ratio of the sample is increased. In addition, the influence of temperature, pressure and time for different phthalates has been studied.