Abstract Poly( m-aminophenol) (PmAP) was synthesized by the oxidative polymerization of m-aminophenol in sodium hydroxide medium using ammonium persulfate oxidant at room temperature. The synthesized polymer showed very good solution processability as it was well soluble in aqueous sodium hydroxide, dimethylsulfoxide (DMSO), dymethylformamide (DMF), etc. A free-standing film was cast from thermal evaporation of DMSO solution of the synthesized PmAP. The film was then doped with aqueous sodium hydroxide and methanol mixture by solution doping technique at room temperature. The doping conditions were standardized in terms of the DC-conductivity of the doped film. The doped PmAP was characterized by ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, Electron dispersion spectroscopy, X-ray diffraction spectroscopy, elemental analysis by atomic absorption spectroscopy, thermogravimetric analysis and DC-electrical conductivity. The DC-electrical conductivity of PmAP film was increased to 2.34 × 10 −5 S/cm from <10 −12 S/cm due to sodium ion doping. From all the above characterizations it was confirmed that the sodium ions were not the reason for the conduction. The incorporated sodium cation in the polymer through free –OH groups of the polymer chain was induced the electron cloud of the polymer and so the polymer became conducting.