Additions of PhMe₂SiH to 2-cyclohexen-1-one, 2-cyclopenten-1-one, 4,4-dimethyl-2-cyclohexen-1-one, and cyclohexanone (11) are catalyzed by the rhodium complexes ClRh[P(CH₂CH₂(CF₂)_n − 1CF₃)₃]₃ (1; n = 6, 8), which have very high affinities for fluorous liquid phases. Reactions of the enones are conducted with 0.80 mol% 1 at 60 °C under biphasic conditions in CF₃C₆F₁₁–toluene or monophasic conditions in CF₃C₆F₁₁–hexanes. The reactions are faster under the latter conditions and the catalyst and products are efficiently separated at lower temperatures under biphasic conditions. Distillations of the non-fluorous phases give mixtures of 1,4- and 1,2-hydrosilylation products (>99–92∶<1–8) in 93–88% yields. The catalyst-containing CF₃C₆F₁₁ phases are recycled two times with similar results. Reactions of 11 are studied under analogous conditions (0.2 mol% 1) at 28 and 40 °C and give cyclohexyl dimethylphenylsilyl ether. Rate profiles show induction periods for the first cycle, indicating an irreversible transformation of 1, but not for subsequent cycles. Only minor decreases in activity are observed over four cycles, consistent with little catalyst leaching or decomposition. When catalyst loadings are decreased to 0.02 mol%, TON of 4400 can be obtained.