The use of supercritical carbon dioxide (SCCO2), as a reactional medium for enzymatic reaction, is greatly impeded by the difficulty of using relatively polar substrates. From previous works of the literature about enzymology in organic solvents, we extended to supercritical CO2 two techniques : use of complexation with phenylboronic acid (PBAC) and immobilization of polar substrate on silica gel. Their feasibility was demonstrated through the esterification of oleic acid with glycerol or D-fructose. Significant conversion was observed in both cases, and although mechanisms are not yet elucidated in the case of silica gel adsorption, these first results bring new momentum to supercritical fluid technology applied to enzymatic synthesis.