The influence Of CO2-philicity and -phobicity of hydrogenated surfactants on preparation of reverse micelles in SC CO2 have been investigated for the first time. To this end, we used polyethylene glycol mono n-alkyl ether surfactants of different polar head groups and alkyl tails. Micelles prepared were characterized by dissolving 1-ethyl-4-methoxycarbonyl pyridinium iodide probe and recording its charge-transfer band in UV absorption region. From the transition energy of charge transfer band the polarity of the aqueous core of micelles was determined in terms of solvent polarity scale E-T (30) values.