A thin-film hybrid structure consisting of dye-sensitized TiO2 in combination with polypyrrole (PPy) is developed over indium tin oxide (ITO)-coated glass substrate. The steady-state photoconductivity and current–voltage (J–V) characteristics were recorded in the dark as well as under illumination for the fabricated device having the structure ITO/PPy/TY+TiO2/Al. The current–voltage (J–V) characteristics of the device in the dark are explained by the formation of percolation networks of nano-particles between the electrodes. The device becomes symmetric at high voltage suggesting the electron injection from the electrodes into the conduction band of TiO2 under both bias (reverse and forward) directions and the respective current is controled by charge carrier transport. Photoaction spectra of the device prove that the photogeneration of charge carriers is significantly enhanced and spectrally broadened only if electron transfer from the polymers to the dye is possible. It is also found that the increase in concentration of nano-particles changes the spectral shape of the hybrid structure as well as the photoresponse. These results show that a significant photoresponse can be achieved in hybrid materials of dye-sensitized TiO2 nano-particles dispersed in conducting polymer.