Electrochemical Activation of Diverse Conventional Photoredox Catalysts Induces Potent Photoreductant Activity **

Abstract Herein, we disclose that electrochemical stimulation induces new photocatalytic activity from a range of structurally diverse conventional photocatalysts. These studies uncover a new electron‐primed photoredox catalyst capable of promoting the reductive cleavage of strong C(sp 2 )−N and C(sp 2 )−O bonds. We illustrate several examples of the synthetic utility of these deeply reducing but otherwise safe and mild catalytic conditions. Finally, we employ electrochemical current measurements to perform a reaction progress kinetic analysis. This technique reveals that the improved activity of this new system is a consequence of an enhanced catalyst stability profile.