This paper presents a new preparation method of SiO₂ and Al₂O₃via a sol–gel route with CO₂ as a pH regulator. The influence of carbon dioxide as a pH moderator on the textural parameters is demonstrated. The properties of the oxide xerogels were investigated using SEM, TEM, FT-IR, thermal analysis techniques, and low temperature nitrogen adsorption measurements to describe their structural evolution. The results illustrate differences in the final textural properties of the systems obtained depending on the pH regulator used in the synthesis. The method proposed is doubly beneficial as it eliminates the use of (organic or inorganic) acids and represents an interesting and new application of carbon dioxide.