This critical review covers advances in the field of glycerol-derived solvents, with a particular focus on hazardous solvents substitution issues.
The most recent advances in the use of glycerol and glycerol derivatives as solvents are reviewed. There are an increasing number of examples of the use of glycerol itself as a reaction medium, solvent–reagent or a dispersive medium for a large variety of applications. In the case of glycerol derivatives, new synthetic methods, physico-chemical properties and application examples as solvents are revised. Recent studies in the field of solvent classification, as well as solvent substitution issues, in connection with glycerol derivatives are also discussed in this review.