The electronic transport properties of electrochemically deposited conducting polypyrrole (PPy)/Prussian Blue (PB) bilayer films have been studied by investigating the current-voltage (I-V) characteristics in dark and under white light illumination. The I-V characteristics observed are highly non-linear, both in dark and under illumination. Space charge limited conduction (SCLC) appears to be the dominant process governing the charge transport in such composite film structures which is also seen when these films are being used in photoelectrochemical or electrochromic mode. The sensitization effect appears due to relative ease of transport of the photogenerated carriers as compared the carrier transport in dark. © 2002 Elsevier Science B.V. All rights reserved.