During the past decade, sugaring‐out assisted aqueous biphasic systems (ABSs) have been the focus of extensive research due to their widespread applications in the green extraction, separation and purification of various biomolecules and other value-added substances. Due to the biodegradability, electrical neutrality and non-toxicity of carbohydrates, sugaring-out extraction and sugaring-out effect have shown advantages over salting-out extraction methods, such as being simple, stable, cost-effective, fast detachable, and able to avoid equipment corrosion. There are three types of sugar-based ABSs including organic solvent-sugar, polymer-sugar, and ionic liquid (IL)-sugar ABSs, which have been formed from the sugaring-out of aqueous organic solvent, polymer, and IL solutions, respectively. In this work, we review all the ABSs composed of sugars and organic solvents that have been reported in the literature up to 2023, and databases will be provided for: (1) all the sugars and organic solvents studied so far, (2) the methods used for determination of phase diagrams, (3) the models used for the correlation of the phase diagram data and (4) the different target materials extracted, separated, purified and analyzed using these type of ABSs, along with the composition used to form the ABS. We examine the proposed molecular causes for the formation of these ABSs, as well as the effect of different parameters on the phase diagram and the phase formation capability of these systems. Finally, we also examine four of the main applications of organic solvent-sugar ABSs along with the parameters affecting them: (i) partitioning behavior of biomolecules and other added-value compounds, (ii) extraction of different target molecules from real matrixes, (iii) recovery and removal of organic solvents from aquatic environments and (iv) their use in analytical chemistry. In addition, based on the analysis of the data reported so far, this critical review provides a judicious assessment of the existing literature, and the challenges in the sugaring-out effects previously investigated. The scope of further research is also discussed.
