Photoactive organic semiconductor substrates are envisioned as a novel class of bioelectronic devices that transduce light into stimulating biological signals with relevance for retinal implants or guided cellular differentiation. The direct interface between the semiconductor and the electrolyte gives rise to different competing optoelectronic transduction mechanisms. A detailed understanding of such faradaic or capacitive processes and the underlying material science is necessary to develop and optimize future devices. Here, the problem in organic photoelectrodes is addressed based on a planar p‐n junction containing phthalocyanine (H2Pc) and N,N′‐dimethyl perylenetetracarboxylic diimide (PTCDI). The detailed characterization of photoelectrochemical current transients is combined with spectroscopic measurements, impedance spectroscopy, and local photovoltage measurements to establish a model that predicts quantitatively faradaic or capacitive current transients. The decisive elements of the model are the energy levels present at the interface and the voltage building up in the photoelectrode. The result of the efforts is a comprehensive model of photocapacitive and photofaradaic effects that can be applied to developing wireless bioelectronic photostimulation devices.