To investigate the energy levels, absorption bands, band gap, dominant transport mechanisms, recombination mechanisms and the free carrier life time behavior of poly-dibenzo-18-crown-6, poly-DB18C6, films, the dark electrical conductivity in the temperature range of 200-550 K, the absorbance and photocurrent spectra, the photocurrent -illumination intensity and time dependence at 300 K were studied. The dark electrical conductivity measurements revealed the existence of three energy levels located at 0.93, 0.32 and 0.76 eV below the tails of the conduction band. The main transport mechanism in the dark was found to be due to the thermal excitation of charge carriers and the variable range hopping above and below 260 K, respectively. The photocurrent and absorbance spectra reflect a band gap of 3.9 eV. The photocurrent -illumination intensity dependence reflects the sublinear, linear and supralinear characters indicating the decrease, remaining constant and increase in the free electron life time that in turn show the bimolecular, strong and very strong recombination characters at the surface under the application of low, moderate and high illumination intensity, respectively. A response time of 25.6 s was calculated from the decay Of I-ph-time dependence. (C) 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.