Ion-pair reagents and reversed micelles in supercritical carbon dioxide (SF-CO2) were tested as polar mobile phases for supercritical fluid chromatography (SFC). Dioctylsulphosuccinate sodium salt (DSS) was used as the counter-ion in ion-pair supercritical fluid chromatography (IP-SFC) with a packed silica-gel column. DSS/pentane reversed micelles were used in reversed micelle supercritical fluid chromatography (RM-SFC) with a packed fluoroalkyl silica-gel column. IP-SFC and RM-SFC using DSS was demonstrated for analytical separation of ephedrine alkaloids.