Isotopic enrichment offers structural insights that are not easily accessible with natural abundance isotopic composition. Deuterated cellulose has attracted considerable attention in the field of neutron scattering studies, providing information about the dynamics, structure of cellulose and its interactions with other plant cell wall components. The deuteration of cellulose also allows the analysis of cellulose hydrogen bonds by FTIR or NMR techniques. The chemical structure of cellulose contains both exchangeable hydroxyl and non-exchangeable alkyl hydrogens. Deuterium incorporation can be divided into two classifications: biological route which incorporates both alkyl and hydroxyl bound deuterium, and chemical route which typically replaces hydroxyl-bound exchangeable hydrogen. The biological route involves cultivating plants or microorganisms in a deuterium-enriched medium. The chemical route typically involves an exchange reaction between hydroxyl-bound hydrogen and D2O, often facilitating with an alkaline reagent. This review provides an overview of recent advances in deuteration methods and characterization as well as the application of deuterated cellulose.