Host guest interactions between cyclohexasilane (Si(6)H(12)) and amphiphilic invertible macromolecules based on PEG and sebacic acid in acetonitrile (neither a solvent for cyclohexasilane nor a support for the micellization of amphiphilic invertible macromolecules) have been investigated. Despite the extended conformation of the macromolecules and the absence of self-assembled polymeric domains, a macromolecular amphiphilicity itself contributes to localizing Si(6)H(12) by AIP and thus enables Lewis acid-base interactions between Si(6)H(12) and the AIP carbonyl groups. The obtained results demonstrate an interesting phenomenon in that insoluble Si(6)H(12) can be localized by AIP macromolecules in a medium that does not support the formation of polymeric domains.