Chloroaluminum phthalocyanine films have been sublimed on conducting substrates and have been structurally modified by a 12 h immersion in aqueous solutions at pH 3 containing various salts. Only two types of structural modifications resulting from anion uptake into the film have been observed for the entire range of salts used. They have been labeled transformations I and H according to the changes in the Q band absorbance of the modified Pc. The as‐sublimed is characterized by a Q band with a maximum absorbance at about 735 nm. Modifications of the I‐type display a Q band characterized by the growth of a peak at , while the Q band after H‐type transformations shows two maxima at . The photoelectrochemical activity of films have been measured with before and after transformations. Much variation has been observed from one salt to another. Under white light illumination (35 mW cm−2), as‐sublimed films are characterized by short‐circuit photocurrents of 0.25 to 0.30 mA cm2, while after modifications, ranges from 0.10 to 1.0 mA cm−2. For I‐type transformations, the highest values (0.80 to 0.85 mA cm−2) have been obtained with KI. Part of I− uptaken into the film is oxidized by or generated inside the organic layer by reaction of and H+. A charge transfer between Pc and iodine, as well as the structural reorganization of the crystallites resulting from the uptake of anions in the film, are thought to be responsible for the photoactivity improvement. For H‐type transformations, the highest values (0.8 to 1.0 mA cm−2) have been obtained with , , or . For these salts, the structural reorganization of the crystallites goes along with a drastic change in the film morphology as observed by SEM. The long axis of the crystallites, perpendicular to the substrate for the as‐sublimed film, changes its orientation by 90° to become parallel to the substrate after transformation. The kinetics of this process is very fast, with more than 50% completion of modification after 1 min in contact with the solution. This change in orientation is not observed when an H‐type transformation is induced on films by solutions of salts leading to low photoactivities. From the comparison between absorption and action spectra, it seems that H‐type modifications result in two molecular arrangements with only one (the red‐shifted one) being photoelectrochemically active, in contradiction with I‐type modification where the action spectrum follows the absorption spectrum. TEM shows that the modified films remain crystalline and display the same structure after transformation with all salts except when is used. Besides amorphous regions in variable proportions, from one salt to another, the common structure for H and I‐type films differs from the triclinic slipped stacked structure of as‐sublimed . TEM diffractions fit a monoclinic lattice with, , , and , but a triclinic lattice could be possible too. Slight changes in the parameters are probably due to the presence of anions of various sizes. On the basis of the common crystallographic structure after both kinds of transformations, it is proposed that the molecular arrangements of the photoactive H and I‐types are very similar and the difference is only related to the kind of anions incorporated into the films.