This paper describes the synthesis and characterization of novel type AB 2 Y-shaped miktoarm star conductive polyaniline-modified poly(ethylene glycol) [PEG-b-(PANI) 2 ], and preparation of its electrospun nanofiber blend with poly(3-caprolactone) [PEG-b-(PANI) 2 /PCL]. The chemical structures of all samples as representatives were characterized by means of Fourier transform infrared (FTIR), and 1 H nuclear magnetic resonance (NMR) spectroscopies. The molecular weights of PANI segment(s), and miktoarm star conductive PEG-b-(PANI) 2 were found to be 3720, and 5847, respectively, from 1 H NMR spectroscopy. Moreover, electrical conductivities, electroactivities, thermal behaviors, morphologies, and compositions of the synthesized samples were studied. The conductivity and electroactivity measurements showed that PEG-b-(PANI) 2 and PEG-b-(PANI) 2 /PCL electrospun blend nanofibers have lower electrical conductivity and electroactivity than those of the pure PANI. However, the lower electrical conductivity and electroactivity levels in these materials can be improved at the price of solubility, processability, and biocompatibility. Field emission scanning electron microscopy (FE-SEM) images showed that the PEG-b-(PANI) 2 /PCL electrospun nanofibers have a single phase, indicating good interactions between the blend components. The average diameters of these fibers were in the size range of 70 AE 10 nm, and there was no formation of beaded structures in comparison with electrospun fibers of pure PCL. As results, we predicted the synthesized PEG-b-(PANI) 2 and PEG-b-(PANI) 2 /PCL can be used in the biomedical fields such as in conductive scaffolds to promote neurite outgrowth, and nerve regeneration.Scheme 1 Synthetic route of the AB 2 Y-shaped miktoarm star conductive polyaniline-modified poly(ethylene glycol).36718 | RSC Adv., 2015, 5, 36715-36726This journal is