High-performance photoswitches, a key element in organic optoelectronics, are constructed by spin-coating nanogap gold electrodes with the title polymer blend (see figure). Optimizing the gap width of the electrodes gives an on/off ratio of up to 10000 at 1 mV bias. The high on/off ratio, low energy consumption, low cost, simple processing procedures, and high air stability of the photoswitches indicate bright prospects for them in organic optoelectronics.