A hybrid composite was prepared by the formation of poly (3,4-ethylenedioxythiophene) (PEDOT) layer on two types of ordered mesoporous carbon (OMC) by vapor phase polymerization. The morphology, chemical composition, pore structure, and electrical properties of the normal type ordered mesoporous carbon (NTOMC) and rod type ordered mesoporous carbon (RTOMC) composites were compared and analyzed. The surface morphology of the PEDOT-OMC composite did not change, due to the uniform coating of PEDOT layer on the OMC. The content of PEDOT in the composite and the thickness of the coating layer both increased with the amount of the oxidizing agent, Iron (III) p-toluenesulfonate (FTS) used in VPP. Pore size, porosity, and surface area of PEDOT-OMC composite decreased with coating of PEDOT layer on the outer surface of the OMC, and the mesopore inner wall. Electrical resistance decreased with an increase in the thickness of the PEDOT layer coated on the OMC. The PEDOT-RTOMC composite had lower electrical resistivity than the PEDOT-NTOMC composite, suggesting that rod-type morphology is advantageous for electron transport. The capacitance was also higher for the PEDOT-RTOMC than for the PEDOTNTOMC, which is thought to be proportional to the surface area of the composite determined by the external and internal structure of the material.