A combination of ring-opening polymerization and atom-transfer radical polymerization was used to synthesize a four-arm star-shaped poly(epsilon-caprolactone)-b-poly(2-hydroxyethyl methacrylate). The structure of obtained copolymer was determined by Fourier transform infrared, H-1 and C-13 NMR spectroscopies. The uniform electroactive nanofibers consisting blend of four-arm star-shaped poly(epsilon-caprolactone)-b-poly(2-hydroxyethyl methacrylate) copolymer and polyaniline were produced using electrospinning technique. The electroactivity of prepared nanofibers was investigated using cyclic voltammetry measurement. The morphologies of electrospun nanofibers produced from four-arm star-shaped poly(epsilon-caprolactone)-b-poly(2-hydroxyethyl methacrylate) and their blends with polyaniline were investigated by the scanning electron microscopy. The presence of polyaniline resulted in significant decrease of sticking fibers.