Photoelectrochemical properties of multicomponent photoelectrodes based on titanium dioxide and cadmium sulfide powders modified with hexacyanoferrate complexes have been examined. Photocurrent responses were recorded as functions of applied potential and photon energy. Surprisingly, the photocurrent can be switched between positive and negative values as a result of potential or photon energy changes. This new effect called PhotoElectrochemical Photocurrent Switching (PEPS) opens a possibility of new chemical switches and logic gates construction. Boolean logic analysis and a tentative mechanism of the device are discussed.