The ability of [Ru^II(^tButpy)(dmbpy)(MeCN)]²⁺ (1-MeCN) to capture CO₂, with the assistance of triethanolamine (TEOA), has been assessed under photocatalytically-relevant conditions. The photolability of 1-MeCN has proven essential to generate a series of intermediates which only differ by the nature of their monodentate ligand. In DMF, ligand photoexchange of 1-MeCN to give [Ru^II(^tButpy)(dmbpy)(DMF)]²⁺ (1-DMF) proceeds smoothly with a quantum yield of 0.011. However, in the presence of TEOA, this process was disrupted, leading to the formation of a mixture of 1-DMF and [Ru^II(^tButpy)(dmbpy)(TEOA)]⁺ (1-TEOA). An equilibrium constant of 3 was determined. Interestingly, 1-TEOA demonstrated an ability to reversibly catch and release CO₂ making it a potentially crucial intermediate towards CO₂ reduction.