Conductive polymers were obtained by using a new polymerization method where UV-light was used as a photochemical initiator. To obtain high molecular weights, optimum irradiation times were determined. The luminescence properties of polymers have been found to be useful for their identification. The use of luminescence spectroscopy as an analytical technique for polymer identification involves the measurement of fluorescence emission spectrum, which is obtained by exciting the polymer with UV-radiation. Fluorescence emission spectra of polystyrene (PS) and polymethyl methacrylate (PMMA) samples were taken at room temperature at excitation wavelengths at 290 nm and 292 nm, respectively. PPMA was prepared with different molecular weights, and the intensity of the fluorescence emission was correlated with polymer chain length. Conductivity versus molecular weight relation was established for each polymer. The plots obtained between conductivities and molecular weights can be used as a calibration curve. From the plot of emission intensity against polymer molecular weights, the molecular weights of unknown polymeric samples can be determined. The most efficient irradiation times were determined by using conductivity versus irradiation time plots. Conductivity versus temperature change of the polymeric samples at different temperatures was determined. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 119: 1469-1476, 2011