In this contribution, we reported an investigation of the morphologies, surface hydrophobicity, and shape memory properties of the organic-inorganic polyurethanes with double decker silsesquioxane (DDSQ) in the main chains. It was found that the organic-inorganic polyurethanes were microphase-separated and that the POSS cages in the main chains were self-organized into the spherical microdomains with the size of 10-50 nm in diameter. The introduction of POSS cages into the main chains resulted in the enhancement of glass transition temperatures (T-g's). In the meantime, the surface dewettability of the materials was significantly enhanced. X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) indicates the improvement of the surface hydrophobicity resulted from the enrichment of POSS at the surfaces of the polyurethanes. The mechanical analyses, such as dynamic mechanical analysis (DMA) and creep-recovery analysis (CRA), indicate that the POSS microdomains dispersed in the polyurethanes behaved as the physical crosslinking sites and promoted the formation of the crosslinked networks. Owing to the introduction of DDSQ into the main chains, the organic-inorganic polyurethanes significantly displayed shape memory properties, in marked contrast to the unmodified and linear polyurethane. The shape memory behavior has been addressed on the formation of the strong physically crosslinked networks in the organic-inorganic polyurethanes.(C) 2018 Wiley Periodicals, Inc.