Molecular acid-base properties are core to understanding chemical systems and the prediction of reactivity. This axiom holds for cyclopropenium ions in terms of their broad use as (organo)catalysts, ligands, redox-flow batteries, and applications in materials sciences. In view of this significant status, and with it, the critical importance of acidity, we disclose in this report the first comprehensive computational study of the pKa values of cyclopropenium ions employing a subset of 70 structurally diverse cyclopropenium derivatives, density functional computations, and Hammett linear free-energy relationships. Capitalizing upon these computed findings, and with an eye toward greenhouse gas trapping, we further document the timely use of a cyclopropenium-cyclopropenylidene coupled platform for CO2 capture and light-triggered release.