In this work, we synthesized a novel organic–inorganic semitelechelic polymer from polyhedral oligomeric silsesquioxane (POSS) and poly(acrylate amide) (PAA) via reversible addition-fragmentation chain transfer (RAFT) polymerization. The organic–inorganic semitelechelic polymers have been characterized by means of nuclear magnetic resonance spectroscopy, thermal gravimetric analysis, and dynamic mechanical thermal analysis. It was found that capping POSS groups to the single ends of PAA chains caused a series of significant changes in the morphologies and thermomechanical properties of the polymer. The organic–inorganic semitelechelics were microphase-separated; the POSS microdomains were formed via the POSS–POSS interactions. In a selective solvent (e.g., methanol), the organic–inorganic semitelechelics can be self-assembled into the micelle-like nanoobjects. Compared to plain PAA, the POSS-capped PAAs significantly displayed improved surface hydrophobicity as evidenced by the measurements of static contact angles and surface atomic force microscopy. More importantly, the organic–inorganic semitelechelics displayed typical shape memory properties, which was in marked contrast to plain PAA. The shape memory behavior is attributable to the formation of the physically cross-linked networks from the combination of the POSS–POSS interactions with the intermolecular hydrogen-bonding interactions in the organic–inorganic semitelechelics.