Although excellent candidate solvents for cellulose, capa-ble of dissolving 20 wt% of the carbohydrate for electro-spinning processes, dialky-limidazolium carboxylate ionic liquids undergo unde-sirable side reactions with the reducing end of saccharides, terminating in an equilibrium concentration of a 2-(hydroxymethyl)-substituted imidazolium ‘adduct’. The addition of small molar quantities of a benign, non-toxic and inexpensive co-solvent, e.g. glycerol, mini-mises the rate of adduct ac-cumulation, thereby enhanc-ing the long-term thermal stability and recyclability of the expensive ionic liquid component. NMR, UV-vis and mass spectrometry ex-periments reveal that the im-proved stability is likely at-tributable to suppression of the transient dialkylimidazol-2-ylidene carbene, via hy-drogen-donation by the pro-tic co-solvent, rather than by cyclic acetal protection of the carbohydrate. The incor-poration of (up to) 10 wt% of glycerol into the solvent mix-ture does not exacerbate the rate of cellulose depolymeri-sation compared to in the neat ionic liquid, and high solubility of cellulose is main-tained. Furthermore, a col-ourimetric comparison of the recovered solvents, following cellulose re-precipitation, demonstrates that glycerol does not increase the concen-tration of contaminant re-ducing sugars in the organic electrolyte.