We report here, as an example of actual photointercalation, the light‐induced intercalation of copper into p‐type from an organic medium . The two types of electrodes used had their exposed surfaces parallel or perpendicular to the cleavage surface [(001) plane]. From the photovoltages, short‐circuit currents, current vs. potential characteristics, photocurrent spectra, and SIMS measurements, it is shown that metallic copper is photoelectrodeposited on the cleavage surface whereas copper is photointercalated when the surface perpendicular to the cleavage face is in contact with the electrolyte. Deintercalation of copper does not take place spontaneously in the dark.