epsilon-Caprolactone was polymerized by ring-opening polymerization (ROP), using thiophene methanol as the initiator and stannous octoate as the catalyst to yield poly(epsilon-caprolactone) with a thiophene end group. Homopolymerization of thiophene functionalized poly (epsilon-caprolactone) (PCL) was achieved by a constant current electrolysis method. Copolymerizations of PCL with thiophene and pyrrole were achieved in acetonitrile (ACN)-tetrabutylammonium tetrafluoroborate (TBAFB) solvent-electrolyte couple via constant potential electrolysis. Characterization of the samples were performed by nuclear magnetic resonance spectroscopy (NMR), cyclic voltammetry (CV), fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy, (SEM). Electrical conductivities were measured by the four-probe technique. Spectroelectrochemical behavior of PCL/PTh film, which was deposited on ITO-glass, was investigated by UV-Vis Spectrophotometer. Furthermore, it is found to be an anodically coloring copolymer that electrochemically sit-itches between gray-blue oxidized state and pole red reduced state, exhibiting electrochromic behavior.