Rhodium metal catalyst was used in the field of NBR homogeneous hydrogenation. A new extraction method of noble metal rhodium catalyst recovery from hydrogenated NBR (HNBR) solution has been researched. Rhodium metal catalyst can be efficiently removed from HNBR solution using SnCl2 as ligand and HCl as extractant. The condition of removing rhodium catalysts from HNBR solution has been studied, including reaction temperature, reaction time, SnCl2 concentration and proportion of aqueous phase to organic phase, and the removal of the rhodium metal catalyst is over 99% under the best conditions. IR and 1H NMR characterization show that HNBR structure and nitrile group have no change after rhodium metal catalyst is removed from HNBR solution.