Deep eutectic solvents (DESs) have garnered increasing attention as sustainable solvents for natural polysaccharides. Galactomannans (especially guar and locust bean gums) are abundant natural compounds used in food, medicine, agriculture and daily chemical products, whereas their high molecular weight and randomly distributed non-linear structures remain a huge challenge in solubilization and high value-added utilization. In this study, the dissolution of galactomannans in type II/III DESs was comprehensively investigated using density functional theory (DFT) calculation, experimental results, and molecular dynamics simulation (MD). The results indicated that immense anionic and neutral H-bonds supported by type II DESs (consisting of a quaternary ammonium salt and a metal chloride hydrate) could break and rebuild galactomannan H-bond networks, thereby exhibiting remarkable physical solubilization. A large number of active acid sites in type III DESs (consisting of a quaternary ammonium salt and a hydrogen bond donor) greatly improved solubility and cleaved the glycosidic bond, enabling the recovery of polysaccharides with a target molecular weight. Furthermore, significant correlations between solubility and the structure of galactomannans had been established, which meant that high molecular weight and rich galactose side-chains produced repulsive interactions with DESs, directly hindering dissolution. Overall, this work not only offered a framework for enhancing the dissolution of polysaccharides, but also proposed a promising strategy for development of task specific DESs promoting green chemistry and the use of sustainable bioresources.