In this investigation, Al/PEDOT/C/p-Si structure has been fabricated by synthesizing PEDOT/C composites on the p-Si substrate. The thickness and surface morphology of PEDOT/C on p-Si have been investigated by using the scanning electron microscope. The optical characterization of PEDOT/C solution indicated a strong optical absorbance peak located at 267 nm. The electrical characterization of Al/PEDOT/C/p-Si structure was made under dark and illumination conditions at the room temperature. The ideality factor, and barrier height were identified to be 1.28, 1.12 and 0.80 eV, 0.83 eV from current-voltage (I-V) measurements for dark and illuminated conditions, respectively. The results show that the Al/PEDOT/C/p-Si structure may be utilized to be a photodiode in optoelectronic implementations.