A series of fluorinated calixarene derivatives, with lower rim sulfur-donor atoms, were synthesized and studied for the sequestration of gold using supercritical fluid extraction. Following temperature and pressure optimization and using extracts collected in methyliso-butyl ketone, analysis by flame atomic absorption spectrometry reveals that Au(III) can be efficiently complexed and extracted by a novel calix[4]arene thiourea reagent in supercritical CO2.