Abstract: Cellulose is the most abundant biopolymer on earth and is widely exploited for industrial purposes. It is found in the extracellular matrices of urochordates (a unique example among animals), bacteria, algae and all members of the plant kingdom. The structure of cellulose consists of a linear chain of several hundred to over ten thousand 4- linked β-D-glucose units, with chains combined into fibers. To accurately investigate the supramolecular structures of cellulose, and its derivatives or extractions from different organisms, Nuclear Magnetic Resonance (NMR) experiments are indispensable. This review will describe the current application of NMR to this polysaccharide utilizing data published within the last decade. It will cover the structure of native cellulose and its derivatives (mainly low-molecular weight oligomers) from different types of preparation, including aqueous solution, ionic liquids, solid-state, complexes with other molecules, and microfibrils. Most of these data come from plant and bacterial cell wall celluloses, although some information will be extracted from the study of red algal cell wall molecules. NMR monitoring also has been used to document the cellulolytic activity of rumen bacteria. These interesting observations which reveal how the composition and structure of cellulose is changed during its metabolism of degradation will be discussed. In solid-state NMR, cellulose appears in two crystallite allomorph forms (Iα and Iβ) that have different structural properties and vary proportionately in relation to the type of the organism studied. Solid-state 13C-NMR experiments are the most widely used NMR methods for structural analyses. Cross-Polarization/Magic Angle Spinning (CP/MAS) is largely employed in order to provide high resolution spectra. Other useful NMR methods involve spin-diffusion analyses, isotopic labeling, anisotropic data, spin-relaxation time calculations and scalar coupling constant values. These data contribute to understanding the structure of cellulose, its dynamic behavior, molecular ordering, mechanism of its dissolution, and interactions with other molecules. This compilation is intended to provide an overview of the diverse types of information available from NMR, and their usefulness in describing this important polymer.