Here we report a highly active and selective hydroformylation of 1-octene in ionic liquid (IL)/MeOH system based on a zwitterionic phosphine ligand bearing a lysine moiety (L(NH2)COOH). The Rh-catalyst grafted lysine in the form of ammonium salt ([Rh-L(NH3 (+))COOH]Tf2N) was successfully immobilized in the IL [bmim]Tf2N and recycled for seventeen times without significant loss of activity, selectivity and Rh catalysts. This study has provided a novel strategy for efficient separation and recycling of Rh catalysts.