Supercritical fluid extraction (SCFE), based on the utilization of a fluid under supercritical conditions, is a technology suitable for extraction and purification of a variety of compounds, particularly those that have low volatility and/or are susceptible to thermal degradation. The interest in SCFE is promoted by legal limitations of conventional solvents for food and pharmaceutical uses. The physicochemical properties of supercritical CO2 (higher diffusivity, lower viscosity, and lower surface tension than conventional solvents) facilitate mass transfer and allow an environmentally friendly operation. This article presents a comprehensive compilation of data on the supercritical CO2 extraction of antioxidant compounds from vegetal materials, with particular attention to those of a phenolic nature. Aspects concerning the supercritical operation for extraction and fractionation of antioxidants compounds are considered, including equilibrium solubility of pure compounds and effects of the operational conditions on the antioxidant activity of isolated fractions. The data are compared to those reported for synthetic antioxidants and natural extracts obtained by conventional solvent extraction from vegetal matrices.