The application of polyoxometalate (POM) as building blocks to construct chiral POM-based functionalized frameworks remains a long-standing challenge. In this study, we report a chiral assembly by blending inorganic POMs and organic cyclodextrin (α-CD) molecules on the basis of coordination interactions. {SiW₁₂} anions connect with Mn ions (Mn²⁺) antiparallel to form a unique all-inorganic layer with significant voids. The similar α-CD layered structure fills the voids of the POM–Mn layers, which are interwoven to form an organic–inorganic hybrid, which is extended by Na⁺ ions to produce a three-dimensional framework. The stability, chiral separation, chiral catalysis, and proton conductivity of this composite framework are explored.