In this chapter, supercritical fluid extraction and fractionation of natural oil mixtures are presented as an alternative to traditional methods like steam distillation, liquid solvent extraction, or vacuum distillation. In the search of alternatives to traditional methods, the principles of phase equilibrium engineering are followed to analyze the SCF extraction and continuous fractionation of natural products. The fundamentals of these high pressure technologies, which combine the principles of distillation and extractive distillation, are presented together with the limitation of simple countercurrent fractionation, which in the end justifies the need of external reflux. Through several case studies, the optimization and solvent selection are analyzed for processes in which the fractionation is driven by the pressure, temperature, and flow rate of the SCF.