Utilizing light is a smart way to fuel chemical transformations as it allows the energy to be selectively focused on certain molecules. Many reactions involving electronically excited species proceed via open‐shell intermediates, which offer novel and unique routes to expand the hitherto used synthetic toolbox in organic chemistry. The direct conversion of non‐prefunctionalized, less activated compounds is a highly desirable goal to pave the way towards more sustainable and atom‐economic chemical processes. Photoexcited closed‐shell anions have been shown to reach extreme potentials in single electron transfer reactions and reveal unusual excited‐state reactivity. It is, therefore, surprising that their use as a reagent or photocatalyst is limited to a few examples. In this Review, we briefly discuss the characteristics of anionic photochemistry, highlight pioneering work, and show recent progress which has been made by utilizing photoexcited anionic species in organic synthesis.