This Review describes recent progress in the self-assembly of organic/inorganic POSS hybrids derived from mono-, di-, and multi-functionalized POSS cages. We highlight the self-assembled structures and physical properties of giant surfactants and chain-end- and side-chain-type hybrids derived from mono-functionalized POSS cages; main-chain-type hybrids derived from di-functionalized POSS cages; and star-shaped hybrids derived from multi-functionalized POSS cages; with various polymeric attachments, including polystyrene, poly(methyl methacrylate), phenolic, PVPh, and polypeptides.