A new mwthod has been used for the preparation of poly-p-phenylene. The preparative approach include coupling of arylmagnesium bromide, generating from dibromobenzene, by electron transfer to 2,3-dichloropropene at room temperature. The reaction product was identified by infrared spectrum. The very strong absorption band at 806 cm−1 (ν para) in the infrared spectrum of poly-p-phenylene showed the para position linked benzene ring. The relative absorption intensity ratio of ν para to that of out-of-plane vibration band (ν1) due to terminal phenyl group indicating that poly-pphenylene obtained here has high degree of polymerization. The poly-p-phenylene has been doped with iodine and hydoriodic acid to form dark brown to black powder. The chemical and physical properties of these charge transfer complexes have been characterized by elemental analysis, infrared spectra, diffuse reflectance electronic spectra, electron spin resonance spectra, magnetic susceptibility measurement and electrical conductivity measurement. All the doped polymers have electrical conductivity in the range of 10−6 to 10−7 Scm−1 with thermally activating semiconductor properties.