New block copolymers Polystyrene-b-poly (2,2,2-trifluoroethyl acrylate)-b-Polystyrene (PS-PTFEA-PS) with controlled molecular weight (M-n=5000-11000 gmol(-1)) and narrow molecular weight distribution (M-w/M-n=1.13-1.17) were synthesized via RAFT polymerization. The molecular structure and component of PS-PTFEA-PS block copolymers were characterized through H-1 NMR, F-19 NMR, GPC, FT-IR and elemental analysis. The porous films of such copolymers with average pore size of 0.80-1.34 m and good regularity were fabricated via a static breath-figure (BF) process. The effects of solvent, temperature, and polymer concentration on the surface morphology of such film were investigated. In addition, microstructured spheres and fibers of such block copolymers were fabricated by electrospinning process and observed by scanning electron microscopy (SEM). Furthermore, the hydrophobicity of porous films, spheres, and fibers was investigated. The porous film showed a good hydrophobicity with the water-droplet contact angles of 129 degrees, and the fibers showed higher hydrophobicity with the water-droplet contact angles of 142 degrees. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 678-685