Optically active (S)-(+)- and (R)-(-)-10,10'- spirobi [10H-phenoxasilin]-1,1'-diols were synthesized by the transesterification of their optically active di-p-toluoyl derivatives resolved by chiral HPLC. The absolute configurations of the optically active spirosilanes were elucidated by single-crystal X-ray structural analysis. Phosphoramidite derivatives of the optically active diols were applied to Pd-catalyzed asymmetric allylic amination using 1,3-diphenylallyl acetate and benzylamine with moderate enantioselectivity.