Poly(2,2,2-trifluoroethyl acrylate)-block-poly(glycidyl methacrylate) (PTFEA-b-PGMA) diblock copolymer was synthesized via sequential reversible addition-fragmentation chain transfer (RAFT) polymerization. The reactive diblock copolymer was incorporated into epoxy to obtain the nanostructured thermosets. The morphology of the thermosets was investigated by means of atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS). It is identified that the demixing of the reactive subchain (viz. PGMA) out of epoxy matrix occurred in the process of curing reaction, which exerted a profound impact on the glass transition temperatures of the nanostructured thermosets. The static contact angle measurements showed that the nanostructured thermosets displayed a significant enhancement in surface hydrophobicity as well as a reduction in surface free energy. The improvement in surface properties was attributed to the enrichment of the fluorine-containing block (i.e., PTFEA) of amphiphilic diblock copolymer on the surface of the thermosets, which was further evidenced by surface atomic force microscopy (AFM). The measurement of critical stress intensity factor (K-1C) showed that the fracture toughness of the materials was significantly enhanced by the inclusion of a small amount of PTFEA-b-PGMA diblock copolymer. (C) 2011 Elsevier Ltd. All rights reserved.