In the urgent search for sustainable processing media that would allow for a diverse design of cellulose materials through re-assembly from the dissolved state, aqueous hydroxides remain the most attractive options, combining the sustainable character and large-scale viability with the unique ability to highly activate and solubilize individual cellulose chains. Yet, despite a long history of aqueous hydroxides in cellulose processing and chemistry, cellulose dissolution and behavior in these systems is mechanistically not well-understood. Numerous efforts to elucidate the thermodynamics of cellulose solutions in aqueous hydroxide solutions, point out the eutectic hydrates of the hydroxides as decisive for stabilization of the dissolved polymer, along with the need to prevent the chain-chain interactions through hydrophobic pairing and accomplish a partial deprotonation of cellulose hydroxyls providing an additional (albeit limited) electrostatic stabilization. Moreover, regardless of the nature of the stabilizing forces, their combined effect is, in general, insufficient to overcome the extensive cellulose-cellulose interactions and a low entropy gain of solvatization, why dissolution is restricted to a very narrow range of conditions yielding meta-stable solutions. Our work on these intriguing systems has revolved around gaining mechanistic understanding of critical cellulose-solvent and cellulose-water interactions along with the accompanying entropy and enthalpy contributions to the stabilization of the dissolved state. Elucidating the role of the cation and incorporated CO2 for this stabilization along with developing new hydroxide-based solvents has been in focus. Insights from combining different cations, from modifying their structural features and investigating the CO2 interactions with these systems will be discussed with particular emphasis on the stability of the dissolved state and potential for further development.