Here, we report the development and application of a novel class of spirosilacycle-based diphosphine ligands (SPOSiPs). This type of diphosphine ligand could be readily prepared in two steps with high efficiency starting from enantiopure spirobiphenoxasilin-diol (SPOSiOL). According to the structural analysis of SPOSiP and its PdCl2 complex, SPOSiPs possess a flexible chiral pocket and feature a rigid configuration, a large dihedral angle, a long P-P distance, and a large P-M-P bite angle in their metal complexes. The potentials of SPOSiPs in asymmetric catalysis have also been preliminarily disclosed.