Six model reactions were performed including asymmetric additions of diethylzinc or alkynes to aldehydes in the presence of axially chiral BIPHNOL ligands, Pd-catalyzed asymmetric cycloadditions in the presence of chiral phosphoramidite ligands, and chiral phosphoric acid-catalyzed asymmetric synthesis of 1,1'-spirobiindane-7,7'-diol (SPINOL) derivative and [4+3] cyclization to evaluate reactivity and enantioselectivity of our biphenyl ligands and catalysts. We found that variation of 2,2'-substituent groups could provide different types of ligands and catalysts, and variation of substituent groups at the 3, 3', 5, 5', 6, 6'-positions could make ligands and catalysts more efficient in the asymmetric catalytic synthesis. We believe that our newly developed diverse adjustable axially chiral biphenyldiols will find wide applications in enantioselective catalysis.