Ruthenium and rhodium phosphine complexes catalyze the hydrosilation of olefins in dense carbon dioxide. The incorporation of polyfluorinated phosphine ligands in the conventional hydrosilation catalysts provides enhanced solubility in dense carbon dioxide resulting in a higher catalytic activity and selectivity; the best result was obtained using RuCl2[P(C6H4-p-CF3)3]3. The reaction is applicable to the synthesis of a fluorous silane coupling agent.