A series of A-B type sterically regular bicyclio[3.3.0] diene-based polymers were designed and synthesized as immobilized chiral diene ligands for asymmetric catalysis. With polymeric diene 6b, good to excellent enantiose- lectivities can be achieved in Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to a,β-unsaturated ketones.