Electroactive nanofibers decorated with α,ω-bi-(dinitrophenylcaproic acid), abbreviated as DNP, have been prepared by electrospinning a solution of α,ω-bi[2,4-dinitrophenylcaproic][poly(ethyleneoxide)-b-poly(2-methoxystyrene)-b-poly(ethylene oxide)], polystyrene and single-walled carbon nanotubes (SWCNTs). The α,ω-bi[2,4-dinitrophenylcaproic][poly(ethyleneoxide)-b-poly(2-methoxystyrene)-b-poly(ethyleneoxide)] polymers were synthesized by living anionic polymerization and subsequent esterification to obtain the DNP-functionalized polymers. The nanofibers (300 nm) were electrospun onto a silicon wafer substrate at a voltage of 10 kV using dimethylformamide and chlorobenzene as solvents. The nanofibers were characterized by Raman spectroscopy, fluorescence microscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM) and optical microscopy. The DNP groups, therein, were tethered to the nanofibers via oligo(oxyethylene) spacers. The DNP groups decorating the nanofibers were capable of specifically binding with anti-DNP immunoglobulin E (IgE). The binding specificity of nanofibers containing 1% SWCNTs with anti-DNP IgE was studied via fluorescently labeled (Fluorescein IsoThioCyanate) FITC-IgE. Electronic activity of the nanofibers was studied by I–V plots from Kelvin sensing. The I–V plots before sensitizing with IgE differed from the I–V plots after binding with IgE. The results of the studies suggest the possibility of developing functional nanofibers as the active component in biosensors. Copyright © 2013 John Wiley & Sons, Ltd.