In this article, new perfluorinated binaphthyl Mn(III) complexes have been synthesized by template effect. The synthesized complexes were characterized by elemental analysis, FT-IR, LC/MS, UV-vis spectroscopy. After the solubility of the catalysts in scCO(2) was observed through the high pressure reactor, catalytic activities of the catalysts have been tested in homogeneous asymmetric epoxidation of styrene in both dichloromethane (organic solvent) and supercritical carbon dioxide (scCO(2)). In order to determine and compare to complexes, the effect of synthesized catalysts to conversion and selectivity was investigated. Reaction parameters such as; reaction time, solvent type and position of substituents were also assessed during the analysis. (C) 2013 Elsevier B.V. All rights reserved.