Organic semiconductors have garnered significant interest as key components for flexible, low-cost, and large-area electronics. Hitherto, both materials and processing thereof seems to head towards a mature technology which shall ultimately meet expectations and efforts built up over the past years. However, by its own organic electronics cannot compete or complement the silicon-based electronics in integrating multiple functions in a small area unless novel solutions are brought into play. Photochromic molecules are small organic molecules able to undergo reversible photochemical isomerization between (at least) two (meta)stable states which exhibit markedly different properties. They can be embedded as additional component in organic-based materials ready to be exploited in devices such as OLEDs, OFETs, and OLETs. The structurally controlled incorporation of photochromic molecules can be done at various interfaces of a device, including the electrode/semiconductor or dielectric/semiconductor interface, or even as a binary mixture in the active layer, in order to impart a light responsive nature to the device. This can be accomplished by modulating via a light stimulus fundamental physico-chemical properties such as charge injection and transport in the device.