As fossil fuels remain a major source of energy throughout the world, developing efficient negative emission technologies, such as direct air capture (DAC), which remove carbon dioxide (CO2) from the air, becomes critical for mitigating climate change. Although all DAC processes involve CO2 transport from air into a sorbent/solvent, through an air–solid or air–liquid interface, the fundamental roles the interfaces play in DAC remain poorly understood. Herein, we study the interfacial behavior of amino acid (AA) solvents used in DAC through a combination of vibrational sum frequency generation spectroscopy and molecular dynamics simulations. This study revealed that the absorption of atmospheric CO2 has antagonistic effects on subsequent capture events that are driven by changes in bulk pH and specific ion effects that feedback on surface organization and interactions. Among the three AAs (leucine, valine, and phenylalanine) studied, we identify and separate behaviors from CO2 loading, chemical changes, variations in pH, and specific ion effects that tune structural and chemical degrees of freedom at the air–aqueous interface. The fundamental mechanistic findings described here are anticipated to enable new approaches to DAC based on exploiting interfaces as a tool to address climate change.