A solid-state NMR (SSNMR) study is reported on the effect of temperature on the molecular mobility of amorphous gentiobiose, which is complemented with data obtained from crystalline samples C-13 cross-polarization/magic-angle-spinning (CPMAS) spectra and H-1 MAS spectra were obtained for gentiobiose at natural abundance, in the amorphous state, from 293 K up to the glass transformation region (T-g = 359 K) Two well-defined molecular mobility regimes were observed corresponding to different motional modes NMR results on molecular dynamics are discussed and compared with those obtained by thermally stimulated depolarization currents (TSDC) and dielectric relaxation spectroscopy (DRS) SSNMR spectra presented evidence for a new polymorphic form of gentiobiose not yet reported in the literature which is obtained by slow heating of the amorphous solid up to 364 K inside the NMR zirconia rotor