Three-Component Azidation of Styrene-Type Double Bonds: Light-Switchable Behavior of a Copper Photoredox Catalyst**

[Cu(dap)(2)]Cl effectively catalyzes azide addition from the Zhdankin reagent to styrene-type double bonds, and subsequent addition of a third component to the benzylic position. In the presence of light, a photoredox cycle is implicated with polar components such as methanol or bromide adding to a benzylic cation. In the absence of light, by contrast, double azidation takes place to give diazides. Therefore, regioselective double functionalization can be achieved in good to excellent yields, with a switch between light and dark controlling the degree of azidation.