The 13C chemical shift tensors of two crystalline forms of glucose (α-glucose and α-glucose·H2O) were determined from one-dimensional (1D) and two-dimensional (2D) solid-state nuclear magnetic resonance (NMR) spectroscopy experiments. The experimental values determined from 1D and 2D methods are in very good agreement. Quantum chemical calculations were also carried out using the gauge-including projector augmented wave (GIPAW) method for plane-wave density functional theory (DFT) as implemented in the CAmbridge Serial Total Energy Package (CASTEP). The calculated 13C chemical shifts were found to be in excellent agreement with experimental values for crystal structures that had their hydrogen atoms optimized and after an appropriate calibration was applied to convert calculated chemical shieldings into chemical shifts. The work presented here lays an important foundation for future solid-state NMR and quantum chemical calculation investigations of the various crystalline forms of cellulose.