In this contribution, we report the synthesis of organic–inorganic random polymers from methacrylate-terminated poly(ethylene oxide) (MAPEO) (M_n = 950) and 3-methacryloxypropylheptaphenyl polyhedral oligomeric silsesquioxane (MAPOSS) macromers via reversible addition–fragmentation chain transfer (RAFT) polymerization with 4-cyano-4-(thiobenzoylthio) valeric acid (CTBTVA) as the chain transfer agent. The organic–inorganic random copolymers were characterized by means of ¹H NMR spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The results of GPC indicate that the polymerizations were carried out in a controlled fashion. Transmission electron microscopy (TEM) showed that the organic–inorganic random copolymers in bulk were microphase-separated and the POSS microdomains were formed via POSS–POSS interactions. In aqueous solutions the organic–inorganic random copolymers were capable of self-assembling into spherical nanoobjects as evidenced by transmission electron microscopy (TEM) and dynamic laser scattering (DLS). The self-assembly behavior of the organic–inorganic random copolymers was also found to occur in the mixtures with the precursors of epoxy. The nanostructures were further fixed via subsequent curing reaction and thus the organic–inorganic nanocomposites were obtained. The formation of nanophases in epoxy thermosets was confirmed by transmission electron microscopy (TEM) and dynamic mechanical thermal analysis (DMTA). The organic–inorganic nanocomposites displayed the enhanced surface hydrophobicity as evidenced by surface contact angle measurements.