We carried out an investigation of the Cd‐chalcogenide/ferri‐ferrocyanide photoelectrochemical cells. In particular, the effect of surface morphology and the effect of added salts upon the characteristics of these cells were investigated. Successive etching with (3%)/methanol, aqua regia, and finally photoetching increases the surface roughness of (,) which has a marked effect on the cell characteristics in the ferri‐ferrocyanide electrolyte (and polysulfide electrolyte as well). In contrast with polysulfide electrolyte, added salts decrease the output stability of the cell and the onset potential for the photocurrent, which can be explained by the removal of the physiosorbed ferrocyanide ions from the electrode surface by the ions of the salt. On increasing the surface roughness of the electrode, while keeping the salt concentration unchanged, the output stability and the onset potential were increased. A kinetic model is used to explain these phenomena. Thus, added salts can be used to probe the strength of the adsorption of the active electrolyte on the surface of the photoelectrode. Finally, we report on the surface morphology of and after irradiation in ferri‐ferrocyanide solution and compare our findings to surface morphologies which were observed previously with the help of photoelectrochemical etching (photoetching). It is found that small rectangular crystallites, probably of cadmium ferrocyanide, deposit on the crystal surface during the photocorrosion process in addition to elemental .