The narrow dissolution window for cellulose in NaOH(aq) is a limiting factor in the production of regenerated cellulose materials, which is why understanding of the molecular interactions in this solvent system is of the highest importance. In this work, we highlight the interaction between cellulose and CO2 in NaOH(aq). The model compound methyl α-D-glycopyranoside (MeO-Glcp) was used to compare the difference of the dissolved state in NaCl(aq) and NaOH(aq), including both pre and post-dissolution addition of CO2. N MR a nd A TR-IR  spectroscopy as well as ocular observations were used in the evaluation.  1H and 13C NMR spectroscopy showed a clear change in chemical shift of the MeO-Glcp when dissolved in NaOH(aq) compared to NaCl(aq), which is a result of deprotonation. Interestingly, the addition of CO2 either pre or post-dissolution of MeO-Glcp in NaOH(aq) affected the chemical shifts differently (apart from the expected change in pH). With quantitative 13C NMR measurements, the uptake of CO2 was found to be more than twice as high when the CO2 was added post-dissolution of MeO-Glcp in NaOH(aq) compared to prior to dissolution. This suggests that specific interactions occur between CO2 and MeO-Glcp when the latter is dissolved prior to the addition of CO2, which could be attributed to the deprotonated state of MeO-Glcp. Furthermore, the dissolved state of cellulose in NaOH(aq) was visually shown to iffer in terms of pre or post-dissolution addition of CO2. Post-dissolution addition of CO2 resulted in the formation of a gelled structure when solutions was left to age in room temperature for two weeks. ATR-IR spectroscopy of materials regenerated from the aged solutions confirmed the introduction of a n ew waveband corresponding to CO2 out-of-phase stretching confirming the sorption of CO2 on cellulose when dissolved in NaOH(aq).