The synthesis of a novel type of chiral spiro monophosphite-olefin (SMPO) ligands based on a hexamethyl-1,1'-spirobiindane scaffold was accomplished starting from Bisphenol C. The optimal ligand could serve as an elegant chiral bidentate ligand in the Rh-catalyzed asymmetric 1,2-addition of organoboronic acids to various acyclic/cyclic aldimines, leading to chiral amines with high yields and excellent enantioselectivities. Detailed stereochemical models for enantioselective induction were elucidated through DFT calculations and postulated the origins of the higher enantioselectivity of phosphite-olefin ligands.