Homogeneous catalytic activation of the strong carbon-fluorine bonds under mild conditions was achieved with the use of rhodium complexes as catalysts. The catalytic reactions between polyfluorobenzenes and hydrosilanes result in substitution of fluorine atoms by hydrogen atoms and are chemo- and regioselective. With individual stoichiometric steps observed and combined, and with intermediates isolated and fully characterized (including crystal structures), these systems demonstrate the effectiveness of a rational approach to catalytic design.