Supercritical CO2 extraction from microalgae is applied with the aim of obtaining an oil rich in alpha-linolenic (ALA) essential fatty acid and with a low omega 6:omega 3 ratio. The maximum extraction yield is obtained at 60 degrees C and 30 MPa with 0.4 kg/h of CO2 and 5% of co-solvent (ethanol). When the effect of pressure, temperature and density on the supercritical extraction yield and solubility are studied, the thermodynamic crossover is found at a pressure close to 30 MPa, while the extraction cross-over occurs at around 25 MPa. The experimental solubility data are correlated by literature empirical models. Mathematical models developed by Sovova are applied to describe the experimental extraction curves. Soxhlet extraction of lipids is also carried out, obtaining a similar fatty acids profile but proving to be less selective than SCCO2 method. Among the three species of microalgae examined, results show that Scenedesmus obliquus oil is richer in omega-3 fatty acids and ALA than Chlorella protothecoides and Nannochloropsis sauna lipids. The effect of the extraction parameters on ALA content and the fatty acid profile is also analysed, concluding that the omega-3 percentage is favoured by lower temperatures, lower pressures and shorter extraction times. (C) 2014 Elsevier B.V. All rights reserved.