The first examples of anion radical cycloaddition induced by homogeneous electron transfer from chemical agents are described. Specifically, upon exposure to chrysene anion radical, bis(enone) substrates are found to engage in stereoselective intramolecular [2 + 2] cycloaddition. These studies, along with the corresponding electrochemically initiated reactions, provide insight into this fundamentally new pattern of reactivity and support the feasibility of expanding this novel reaction type.