The incessant effort to perform a more sustainable chemistry has brought about the development of new materials that accomplish the principles of the green chemistry. In this context, deep eutectic solvents (DESs) have surged as one of the most promising alternatives to the use of toxic organic solvents. Their unique properties have led to a huge development of these materials and a sharp increase of their applications in the recent years in analytical chemistry. They have been applied in sample preparation and analytical techniques. The quantity of new information generated from studies associated with DESs is enormous and needs to be continuously revised. In this review, the most relevant aspects related to the application of DESs in the last five years (2016–2020) have been compiled and critically discussed in order to provide a global view about the advantages and limitations of these new materials in the area of analytical chemistry. •DESs characteristics make them ideal as green materials in analytical chemistry.•Different DESs (NADESs, THEDESs and polyDESs) have been used in analytical chemistry.•DESs have been used in sorbent-based and solvent-based sample preparation procedures.•DESs have been used in chromatographic and electrophoretic techniques.•Further studies are needed to understand synthesis and action mechanisms of DESs.