Brush copolymer of poly (aniline)-g-poly (2-hydroxyethyl methacrylate-g-poly (epsilon-caprolactone)) (PANI-g-P (HEMA-g-PCL)) was synthesized via ring-opening polymerization of epsilon-caprolactone (CL) initiated by poly (aniline)-g-poly (2-hydroxyethyl methacrylate) (PANI-g-PHEMA) macromolecular initiator. The macroinitiator was synthesized by atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate using a polyaniline backbone. Both macroinitiator and graft copolymer were characterized by FTIR and H-1 NMR spectroscopy. The thermal behavior, morphology, and electroactivity of brush copolymer were also investigated by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and cyclic voltammetry (CV), respectively. Uniform nanofibers consisting of blends of (PANI-g-P (HEMA-g-PCL)) copolymer and polycaprolactone (PCL) 10 % with feed ratios of (50/50), (40/60) and (30/70) were prepared using the electrospinning technique. The cyclic voltammetry measurement of blends confirmed the preparation of electroactive nanofibers. The presence of copolymer enhanced the spinnability of solution and significantly reduced the bead formation. This novel system opens up new and interesting opportunities for applications such as electroactive scaffold for tissue engineering.