Quaternary ammonium (QA)-based polymeric sorbents are known to be effective for CO₂ capture, especially from ultradilute streams like air. In this work, we address two major challenges in QA sorbent design for application in moisture-swing processes, porosity control and hydrophilicity modulation. Facilely substituting porous CO₂-active components for non-porous ones can enhance the sorption kinetics by 4-fold compared to the state-of-art, and micro–mesoporous structures are identified as optimal porous structures. A method to modulate the hydrophilicity of QA-based sorbents is developed using controlled radical polymerization, incorporating fluorine-containing monomers. The CO₂ sorption capacity and the tolerance towards moisture are simultaneously enhanced via adjustment of the structure and the content of fluorine-containing blocks. We postulate that porosity and hydrophilicity optimization can make QA-based sorbents adaptive to deployment of scalable moisture-swing processes in varied and complex atmospheric circumstances.