This study reports on two multicomponent hybrid supramolecular assemblies by integrating polyoxometalates (POMs) and cyclodextrins (CDs) through noncovalent interactions, namely, (NH4)KH[{FeMo6(OH)6O18}(γ-CD)]·26H2O (denoted as {FeMo6}(γ-CD), 1) and (NH4)3KH[{FeMo6(OH)6O18}{Mo6O19}(γ-CD)2]·29H2O (denoted as {Mo6}{FeMo6}(γ-CD)2, 2). 1 represents a two-component open framework built from Anderson-type {FeMo6} units by interacting with the external surface of γ-CD while 2 could be viewed as a three-component hybrid when inner cavities of (γ-CD)2 species in 1 are filled by the in situ formed Lindqvist-type {Mo6O19}2- anions driven by a chaotropic effect. This pair of hybrid supramolecular assemblies provides a molecular-level platform for exploring the structure-property relationships related to proton conductivity. As expected, the proton conductivity of 2 remains a 3-fold enhancement compared to that of 1, which may be arisen from the increasing numbers of "proton-carrier" molecules due to the introduction of {Mo6O19}2- guest within the macrocyclic host matrix. This work paves the way for engineering multifunctional POM-CD-based supramolecular frameworks featuring tailor-made properties controlled by inorganic POM entities through a chaotropic effect.