Organic electrolyte solutions (OES)-binary mixtures of an ionic liquid (IL) with a neutral polar aprotic co-solvent-are being recognized as excellent candidate solvents for the dissolution, derivatization, and sustainable processing of cellulose. These solutions exhibit the beneficially combined properties of rapid-to-instantaneous cellulose dissolution, raised thermal stability, and reduced viscosity, compared to cellulose solutions in the parent ILs. Herein, we report the reversible, thermally triggered phase separation of cellulose solutions in 1-ethyl-3-methylimidazolium acetate with 1,3-dimethyl-2-imidazolidinone. In these solutions, cellulose drives the process of phase separation, resulting in a lower, IL-rich layer in which the biopolymer is segregated. In turn, the upper phase is enriched in the neutral co-solvent. We show that the temperature of phase separation can be fine-tuned by modification of mole fractions of IL, co-solvent, and cellulose. This finding holds promise for the design of strategies for separation and solvent recycling in cellulose chemistry. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.