Perfluoroalkyl-substitution of the aryl groups in the BINAPHOS skeleton was achieved using a synthetic strategy based on the Cu(I)-catalyzed cross coupling of arylmagnesium bromide and F(CF 2 ) 6 (CH 2 ) 2 I. The rhodium complexes of the new ligand (R,S)-3-H 2 F 6 -BINAPHOS (10) exhibited spectroscopic properties and reactivities similar to those of the unsubstituted parent compounds. The substitution provided a high affinity of the ligand and its complexes for scCO 2 allowing the development of ecologically benign protocols for catalytic asymmetric synthesis and even the spectroscopic detection of catalytically active intermediates. Using this new system, a large variety of substrates were hydroformylated in scCO 2 with rates and enantioselectivities comparable to those of the parent system in benzene solution. At the same time, the CO 2 -philic substitution pattern resulted in a significantly higher regioselectivity towards the desired chiral aldehydes. Preliminary results indicated for the first time also a remarkable potential of BINAPHOS-derived ligands for asymmetric hydrogenation reactions. The possibility to develop new work-up schemes for product purification and/or catalyst immobilisation based on scCO 2 as the only medium for catalysis and extraction (CESS process) was experimentally verified using a rhodium catalyst containing 10.