Large electrical polarization effects in the time photoresponse of multilayer heterostructure diodes have been observed. This phenomenon manifests itself in a displacement current spike synchronous to a dark–light transition and in an opposite spike in the light–dark one. The effect is associated with the pileup and spatial separation of photogenerated electrons and holes in the wells in the space‐charge region of the diode. At a particular forward bias voltage, the conduction photocurrent is eliminated, allowing accurate measurements of this phenomenon.