Conducting polyaniline-poly(ε-caprolactone) polymer composites were synthesized via in situ deposition techniques. By dissolving different weight percentages of poly(ε-caprolactone) (PCL) (10%, 20%, 30%, 40%, and 50%), the oxidative polymerization of aniline was achieved using ammonium persulfate as an oxidant. FT-IR, UV-vis spectra, and X-ray diffraction studies support a strong interaction between polyaniline (PANI) and PCL. Structural morphology of the PANI-PCL polymer composites was studied using scanned electron microscopy (SEM) and transmittance electron microscopy (TEM), and thermal stability was analyzed by thermogravimetric analysis (TGA) technique. The temperature-dependent DC conductivity of PANI-PCL polymer composite films was studied in the range of 305-475 K, which revealed a semiconducting behavior in the transport properties of the polymer films. Conductivity increased with the increase of PCL in below critical level, however conductivity of the polymer film was decreased with increase of PCL concentration higher than the critical value.