This review surveys advances in the development of various material functionalities based on thermoplastic cellulose and related structural polysaccharide derivatives. First, the dependence of thermal (phase) transition behavior on the molecular composition of simple derivatives is rationalized. Next, approaches enabling effective thermoplasticization and further incorporation of material functionalities into structural polysaccharides are discussed. These approaches include: (a) single-substituent derivatization, (b) derivatization with multi-substituents, (c) blending of simple derivatives with synthetic polymers, and (d) graft copolymerization. Some examples addressing the control of supramolecular structures and the regulation of molecular and segmental orientations for functional materials fabrication, which have especially progressed over the past decade, are also addressed. Attractive material functions include improved mechanical performance, controlled biodegradability, cytocompatiblity, and optical functions.