The CO2/CO32− chemistry of the cellulose/NaOH(aq) solutions has been recently reported to comprise a CO2 incorporation through formation of a transient cellulose carbonate intermediate along with cellulose – CO32− interactions. This work explores on molecular interactions arising when this chemistry is brought together with urea, the most common stabiliser of these solutions. 1H, 13C and steady-state heteronuclear Overhauser effect NMR studies on the cellulose analogues (methyl-β-glucopyranoside (β-MeO-Glcp) and microcrystalline cellulose), combined with pH and ATR-FTIR measurements, reveal concurrent interactions of urea with both CO2 and CO32−– leading to increased uptake of CO2 and a buffering effect. Yet, regardless of the presence of urea, the route of conversion from CO2 to CO32-, whether going through reaction with the carbohydrate alkoxides or OH−, is likely to determine the chemical environment of the formed CO32-. These findings shed a new light on rather overlooked, albeit prominent, interactions in these solutions with the readily absorbed air CO2, essential for further development and implementation, whether towards regenerated and modified cellulose or CO2-capturing concepts.