A highly conductive and three-dimensional electrospun scaffold with proper cell intrusion was developed by virtue of the electrical conductivity of the electrospinning solution. In polyaniline (PANi)/poly (E-caprolactone) (PCL) blend, the weight ratio of PANi to PCL was increased to raise solution conductivity. The electrospun fibers were characterized by microscopy, conductivity and cell culture study. Once ratio of PANi increased from 7% to 70%, the fibers changed from a flat two-dimensional into a three-dimensional structure, and their electrical conductivity increased 1,000 times. Moreover, the cell accessibility of 3D mat greatly overcame that of the 2D mat.