Robust and highly active bimetallic Rh nanoparticle (NP) catalysts, PI/CB Rh/Ag have been developed and applied to the asymmetric 1,4-addition of arylboronic acids to enones without leaching of the metals. We found that the structures of the bimetallic Rh/Ag catalysts and chiral ligands strongly affect their catalytic activity and the amount of metal leaching. PI/CB Rh/Ag could be recycled several times by simple operations while keeping high yields and excellent enantioselectivities. To show the versatility of the PI/CB Rh/Ag catalyst, a one-pot, oxidation-asymmetric 1,4-addition reaction of an allyl alcohol and an arylboronic acid was demonstrated by combining the PI/CB Rh/Ag catalyst with PI/CB Au as an aerobic oxidation catalyst.