Nowadays, computational NMR is widely used for structural and stereochemical studies of a wide series of carbohydrates including mono-, di-, and polysaccharides together with their functional derivatives. Stereochemical analysis of carbohydrates could mostly be performed by using computational versus experimental 1H and 13C-NMR chemical shifts and spin-spin coupling constants in view of their marked stereochemical dependences providing a new guide in stereochemical structure of carbohydrates together with fundamental factors controlling molecular recognition and catalysis in biochemical systems.