CIGS solar cells in many cases show a failure of light/dark superposition of their current-voltage (J-V) curves. Such failure generally becomes more pronounced at lower temperatures. J-V measurements under red light may also show an additional distortion, known historically as the “red kink”. The proposed explanation is that a secondary barrier results from the conduction band offset between CIGS and the commonly employed CdS window layer. This barrier produces a second diode with the same polarity and in series with the primary photodiode. The secondary-diode barrier height is modified by photoinduced changes of trap occupancy in the CdS layer, hence creating a voltage shift between dark and light conditions. Numerical modeling of the proposed explanation, including a band offset consistent with experimental and theoretical values, gives a very good fit to measured light and dark J-V curves over a wide temperature range. It also predicts the observed difference between illuminated J-V curves with photon energy above the CdS band gap, and those with sub-band-gap illumination.