The effect of small concentration of methylene blue dye on photocurrents was studied in the solid-state photoelectrochemical cells fabricated using conducting polypyrrole-coated electrodes sandwiched with solid-polymer electrolyte, namely, polyvinylpyrrolidone with phosphoric acid. A maximum photosensitivity factor (S=ll/ld, where ll is the photocurrent and ld is the dark current) of the order of 5 is observed. The current-voltage (I-V) characteristics in such cells reveal that charge transport is mainly governed by the space charge effect. Comparison of the results presented in this paper with the ones we reported earlier [23] indicates that the matrix in which dye has been incorporated plays an important role in such sensitization processes. A matrix that can efficiently transport the photogenerated charge carriers is observed to be more suitable for such dye-sensitized devices. © 2004 Kluwer Academic Publishers.