A biodegradable five-arm star-shaped polymer based on poly(epsilon-caprolactone) (PCL) was synthesized. Green synthesis of biodegradable star-shaped PCL was performed by Sn(Oct)(2)-catalyzed ring-opening polymerization (ROP) of epsilon-caprolactone (CL) from a glucose core. The chemical structure of star-shaped PCL was investigated by Fourier transform infrared spectroscopy (FTIR), and the average molecular weight of the polymer was determined by (HNMR)-H-1 (about 38,000 g mol(-1)). Thermogravimetric analysis (TGA) curve displayed a main degradation step between 230 and 410 A degrees C where PCL degraded at the maximum rate. The residual mass can be attributed to degradation of the glucose core and its functional groups. Uniform fibers consisting of blends of star-shaped PCL and polyaniline (PANI) were prepared with different feed ratios in a chloroform/dimethylformamide (DMF) solvent system by electrospinning technique. The scanning electron microscopy (SEM) of samples showed the morphology of star-shaped PCL nanofibers with and without PANI. The presence of PANI does not relevantly affect the fiber architecture which shows a slight reduction of the average fiber diameter from 125 to 81 nm and significant decrease of bead formation. Moreover, the cyclic voltammetry (CV) measurement confirmed the preparation of electroactive nanofibers. Here, we combined the advantages of star-shaped PCL with benefits of electrospinning method for obtainment of the uniform nanofibers with possible potential for use in tissue engineering.