This work explores the dynamics of hydrogen bond networks in cellulose through inelastic neutron scattering (INS) and periodic CASTEP calculations. Estimated spectra were based on the crystal structure of cellulose I alpha and I beta and replicate the INS spectrum of cellulose samples with remarkable similarity, allowing a reliable assignment of INS bands to vibrational modes of cellulose. Comparison of cellulose samples from varied sources, from bacterial to kraft pulp, allows the identification of characteristic INS bands, arising from C2-OH torsional motions, which easily identify which allomorph-I alpha or I beta-is prevalent. A high crystallinity index is revealed by the presence of well-defined INS bands associated with highly cooperative CH bending modes along the chain. Hydrating kraft cellulose samples clearly affects those INS bands related with the hydroxymethyl group, identified as the preferred binding site for water molecules. At high humidity content level, a significant proportion of the water molecules is aggregated in clusters within the amorphous cellulose domains. The formation of ice microcrystals leads to a partial disruption of the hydrogen-bond network, as can be concluded from the observed red-shift of the torsional OH vibrational modes. The full assignment and interpretation of cellulose’s INS spectra herein provided is a sound basis for future use of INS spectroscopy in the characterization of functionalized cellulose fibers and composite materials.