Photoelectrochemical effects at chemically deposited CdSe thin films (2000 Angstrom) coupled with as-prepared and air annealed (250 degrees C) CdS films have been investigated by monitoring open-circuit voltage (V-oc) and short-circuit current density (I-sc) at varying incident light intensities and for different heat-treatments temperatures. Two consecutive chemical baths were used in the coupled system. Each bath has been optimized in earlier studies for the deposition of highly photosensitive CdS and CdSe thin films. The photoelectrochemical behavior of single and coupled films was investigated in ferricyanide redox couples. The enhanced short-circuit photocurrent of the as-deposited CdS/CdSe system, despite their lower photosensitivity, indicated that charge separation improved in the coupled system. The role of post-deposition thermal treatments in improving the photoelectrochemical cell characteristics and stability of coupled semiconductors was investigated. Excellent I-V properties were obtained for CdSe and CdS250/CdSe photoelectrodes annealed at 280 degrees C. For the coupled system: V-oc = 960 mV; I-sc = 8.6 mA/cm(2); fill factor (ff) = 0.53 and cell efficiency (eta) = 4.2%. The linearity of V-oc/ln(I-L) and I-sc/I-L plots supports the Schottky-Mott model for these interfaces. The stability of the coupled photoanode is superior to that of the CdSe only-film for the initial 3 h.