Fibers of Polyacrylonitrile/Polyindole were prepared by electrospinning method. Fourier transform infrared spectroscopy (FTIR), Atomic force microscopy (AFM) and Scanning electron microscopy (SEM) were used for their structural characterization. The synthesis and characterization results showed that the incorporation of indole moieties affected the characteristic and topological properties of the polyacrylonitrile fiber. The fiber diameter was closely dependent to the polymer blend solution, surface tension, solution conductivity and viscosity. The results obtained by using Electrochemical impedance spectroscopy (EIS) showed that the fiber diameter affected the electrical conductivity of the fibers. It was discussed that the presence of Polyindole (PIN) content showed an electrocatalytic activity against K3Fe(CN)(6)/K4Fe(CN)(6) depending on the synthetic conditions, preparation process and the structure of organic matrix.