Surface roughness and the associated nanosized voids inside the roughness structures have great influence on the separation performance of thin film composite polyamide reverse osmosis (RO) membranes. Inspired by the recent findings that these voids are formed due to the degassing of CO2 nanobubbles during interfacial polymerization, we systematically investigated the role of carbonate chemistry, particularly the solubility of CO2, in the aqueous m-phenylenediamine (MPD) solution for the first time. "Ridge-and-valley" roughness features were obtained when the pH of the MPD solution was between the two acidity constants of the carbonate system (i.e., 6.3 ≤ pH ≤ 10.3), under which condition HCO3- dominates over the other carbonate species. Increasing pH over this range led to both increased water permeability and better rejection of various solutes, thanks to the simultaneously enhanced effective filtration area and cross-linking degree of the polyamide layer. Further increase of pH to 12.5 resulted in more disparate rejection results due to membrane hydrolysis: rejection of neural solutes (B and As(III)) was compromised whereas that of charged solutes (NaCl and As(V)) was maintained. The mechanistic insights gained in the current study reveal the critical need to design RO membranes directly for end applications based on first principles.