Switchable organic molecules regulated by visible light have attracted attention recently in this context, specifically those that reversibly release protons, such as spiropyran photochromes, which we and others have examined for reversible CO2 capture. By directly converting solar energy and thus avoiding the intermediate generation, storage, and distribution of clean electricity, photochemical separations could eventually be efficient and distributable options for some applications, although dramatic increases in photon utilization, stability, and capture/release kinetics are still required. Furthermore, while photoacids demonstrate important fundamental principles for coupling photoswitching with light-independent equilibria, their inability to operate at high pH is a fundamental limitation inasmuch as they can only capture CO2 from concentrated streams and are likely inapplicable for DAC without additional alkaline sorbents. As part of our research on direct light-driven separations, we considered whether the opposite mode of operation, involving photobases that display reversible photon-induced release of hydroxide, might represent a more promising mechanism for carbon capture. An especially appealing aspect of such a scheme is that the photochemical step (hydroxide release) is unimolecular and CO2-independent and therefore, may proceed with high quantum efficiencies with the judicious design of the photobase.