Non-woven fiber mats were fabricated with the electrospinning method using poly(methyl methacrylate)-co-poly(2-(2-bromoisobutyryloxy) ethyl methacrylate) in various solvents. The surface morphology of the electrospun fibers depended on the solvent vapor pressure and polymer concentration. Surface-initiated atom transfer radical polymerization (ATRP) with 3-(N-2-methacryloyloxyethyl-N,N-dimethyl) ammonatopropanesulfonate), 2-hydroxyethyl methacrylate or 2-(perfluorooctyl)ethyl acrylate generated surface-grafted polymers, as determined by X-ray photoelectron spectroscopy. Scanning electron microscopic observation revealed that the apparent fiber morphology did not change upon modification. The atomic force microscopic images of the grafted fiber cross-sections indicated that monomers and solvents penetrated slightly into the fibers and polymerization occurred at both internal and external initiation sites. Physicochemical properties, such as contact angle, hydrophobicity and hydrophilicity, and wettability, could be altered by the proper selection of substrates (spin-coated flat films or the variously prepared non-woven fiber mats). We have successfully prepared hydrophilic and hydrophobic fiber surfaces by a combination of the electrospinning protocol and surface-initiated ATRP. Polymer Journal (2011) 43, 838-848; doi: 10.1038/pj.2011.80; published online 31 August 2011