A continuous countercurrent supercritical CO2 extraction-distillation dual-column process was developed to extract and concentrate natural vitamin E (VE) from soybean oil deodorizer distillate (SODD). The experimental results demonstrated that process parameters such as extraction pressure, temperature, and solvent-to-feed ratio significantly impacted on the extraction efficiency of natural VE. A new five-parameter mass transfer model for the continuous countercurrent supercritical CO2 extraction-distillation dual-column process was presented based on the Penetration and Double-Film theories. The calculated values of the mathematical model agreed well with the experimental data, with absolute average relative deviation values of less than 25%.