The electrochemical properties of protoporphyrin IX zinc(II) ZnPP films on indium-tin oxide (ITO) substrate have been Studied for three types of films with different arrangements, which were an adsorbed film of ZnPP and LB films of ZnPP and its hybrid with hexadecyltimethylammonium bromide. Cyclic voltammetry (CV) measurement showed that, as the adsorbed amount of ZnPP increases, an irreversible oxidation peak of ZnPP film is intensified. This reveals that electrochemical properties depend on the adsorbed amount rather than the orientation of porphyrin molecules. It was also supported front CV measurement and ultraviolet-visible absorption spectroscopy that porphyrins adsorbed on ITO Substrate were desorbed after the single scan of potential. Additionally, photoresponse of these ZnPP films was investigated by photocurrent measurement. The photocurrent generation is due to carboxylic acid moieties but not ZnPP macrocycles. (C) 2004 Elsevier Inc. All rights reserved.