The conversion of renewable, non-edible and resource-abundant lignocellulose to fuels, chemicals and materials has received significant attention as it holds the possibility of using carbon neutral technologies to combat global changes. Considering the relatively high oxygen content in cellulose, it is more desirable to be transformed into oxygenated chemicals rather than hydrocarbon fuels in view of atom efficiency. Among the oxygen-rich chemicals from biomass, polyols, such as ethylene glycol and propylene glycol, are widely used in polymer synthesis, food industry and manufacturing of pharmaceuticals. Hydrolysis, coupled with hydrogenation and hydrogenolysis serves as an effective approach to transform biomass to polyols. This review summarizes the recent advances in biomass upgrading reactions for the production of polyols with a special emphasis on the formation of glycols.