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The oxidative chemical polymerization of some o-substituted aniline were investigated in hydrochloric acid solution using potassium dichromate as oxidant. All investigated monomers were polymerized except o-nitroaniline, o-sulphonicaniline and o- carboxylicaniline and this behavior was explained by the molecular orbital calculations. The effect of HCl, potassium dichromate and monomer concentrations on the polymerization of each monomer were studied. The effect of temperature on the polymerization rate was investigated for each monomer.The polymers obtained were characterized using different characterization tools such as elemental analysis, XPS, IR, TGA and UV-visible. Some molecular orbital calculations were performed for each monomer and radical cation. Full geometry optimization was performed at Density Functional Theory (DFT) level of theory. The B3LYP method has been adopted using 6-311G basis set.The ac conductivity and dielectric properties were carried out on polymer samples as a function of frequency and temperature. The obtained polymers and their composites with carbon nano-tubes were used to reduce trihalomethanes from drinking water.