As a novel functional layered material, alkali titanates have been widely studied in the fields of catalysis, wastewater treatment, energy storage, and gas sensing. The exchange of alkali metal ions with other functional cations by breaking the ionic bonds between titanium oxide layers is proved to be an effective strategy for the functionalization of alkali titanate. Herein, based on theoretical simulations and experimental studies, for the first time, it is found out that the introduction of CO2 in the interlayer confinement space of potassium titanate can lead to tensile stress and it can help the exchange of H+/K+. Therefore, this work provides a new efficient based on stress engineering to break the ionic bonds and realize the ion‐exchange process of alkali titanates.