AbstractOne of the grand challenges underlying current direct air capture (DAC) technologies relates to the intensive energy cost for sorbent regeneration and CO₂ release, making the massive scale (GtCO₂/year) deployment required to have a positive impact on climate change economically unfeasible. This challenge underscores the critical need to develop new DAC processes with substantially reduced regeneration energies. Here, we report a photochemically‐driven approach for CO₂ release by exploiting the unique properties of an indazole metastable‐state photoacid (mPAH). Our measurements on simulated and amino acid‐based DAC systems revealed the potential of mPAH to be used for CO₂ release cycles by regulating pH changes and associated isomers driven by light. Upon irradiating with moderate intensity light, a ≈55 % and ≈68 % to ≈78 % conversion of total inorganic carbon to CO₂ was found for the simulated and amino acid‐based DAC systems, respectively. Our results confirm the feasibility of on‐demand CO₂ release under ambient conditions using light instead of heat, thereby providing an energy efficient pathway for the regeneration of DAC sorbents.