The establishment of the place of Deep Eutectic Solvents (DESs) as a new class of green solvents was essentially grounded on naïve comparisons with Ionic Liquids (ILs), since both are composed of charged compounds. The easiness of DESs’ preparation afforded the quick preparation and utilization of a massive number of solvents and their use in wide variety of applications with minimal fundamental knowledge of their thermophysical properties and phase equilibria studies. As time went on, the need to define DESs from the thermodynamic point of view and to differentiate them from other classes of solvents was imperative. This perspective review aims at dispelling some myths about DESs through the use of experimental data and computational chemical calculations and establishing fair comparisons with other classes of solvents, ILs, eutectic solvents (ESs) and volatile organic compounds (VOCs), so that clear and sound conclusions can be drawn. Several important parameters typically used to characterize solvents and that have been much used to justify DESs’ wide range of applications, such as vapor pressure, thermal stability, polarity, toxicity and water miscibility, were accessed for these different solvents and comparisons were established. Moreover, a comparative analysis in a selected research area, biopolymer dissolution and treatment, was chosen to illustrate the unique potential of ILs and DESs and the challenges that still need to be addressed. Literature available for the diverse polysaccharides selected (cellulose, hemicellulose and chitin) and lignin highlighted pros and cons and the different level of knowledge gained to date for both ILs and DESs. This part is complemented by recycling and techno-economic considerations for the two classes of solvents, which are additional key aspects to consider for the development of an effective integrated biorefinery process. The conclusion is obvious: DESs are a new class of solvents, with distinct properties from other classes of solvents which are essentially dependent on the properties of their constituent compounds. Therefore, when starting compounds are wisely selected, DESs become an additional and promising pathway in the pursuit of environmentally friendly solvents to replace traditional VOCs for a given application. However, some fundamental studies are still needed to fully understand these systems and define their most effective areas of application.