The electrospun nanofibers of synthetic star-shaped poly(E >-caprolactone) (PCL) and its blends with polyaniline (PANI) were prepared. We utilized the advantages of star-shaped PCL and benefits of electrospinning method for obtainment of the uniform nanofibers with improved properties for tissue engineering. Biodegradable star-shaped PCL with four arms was synthesized by Sn(Oct)(2)-catalyzed ring-opening polymerization (ROP) of E >-caprolactone (CL) from a pentaerythritol core. The chemical structure of star-shaped PCL was investigated by FTIR, and average molecular weight of polymer was determined by (HNMR)-H-1 (about 38000 g mol(-1)). Thermal behavior of star-shaped PCL was also studied by Thermogravimetric Analysis (TGA). Moreover, the cyclic voltammetry (CV) measurement confirmed the preparation of electroactive nanofibers. The scanning electron microscopy (SEM) was also used to investigate the morphology of electrospun nanofibers produced from star-shaped PCL and its blends with PANI with different feed ratios. The presence of PANI resulted in fibers with diameters less than 100 nm and significant decrease of bead formation.