The synthesis of homopolymers based on m-nitroaniline and p-nitroaniline by aniline-initiated ammonium peroxydisulfate oxidation, has been attempted. Poly(m-nitroaniline) and poly(p-nitroaniline), thus synthesized, were characterized by infrared spectroscopy (IR), ultraviolet-visible absorption spectroscopy (UV-vis), H-1 nuclear magnetic resonance spectroscopy (H-1-NMR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and thermal analysis (TG-DTA). The XPS results indicate chemical shifts of different environments for the N 1s, corresponding to the amino and nitro groups. Room temperature conductivities of the HCl-doped homopolymers are very low compared to polyaniline and are of the order of 10(-6) S cm(-1). An attempt has been made to rationalize the results on the basis of the effect of -NO2 substituents on the polymer structure.