A novel and green photochemical polymerization method of N-methylpyrole is reported. Spectral and chromatographic characterizations revealed the formation of high molecular weight polymer (1436 kg/mol) having light absorption in the near-infrared region (~750 nm), high fluorescence emission in the visible region, high conductivity (0.062 S/cm) and good thermal stability. Powder X-ray diffractogram identified a totally amorphous polymer. According to cyclic voltammetry studies the polymer formed (PMPy) possess a relatively low electronic band gap (1.39 eV) which is very important for the (opto)electronic device applications of such materials.