Electrochemically switched 2nd order non-linear optical responses have been demonstrated for the first time in polyoxometalates (POMs), with an arylimido-derivative showing a leading combination of high on/off contrast (94%), high visible transparency, and cyclability. Spectro-electrochemical and TD-DFT studies indicate that the switch-off results from weakened charge transfer (CT) character of the electronic transitions in the reduced state. This represents the first study of an imido-POM reduced state, and demonstrates the potential of POM hybrids as electrochemically activated molecular switches.