As the most abundant natural polymer, cellulose is a prime candidate for the preparation of both sustainable and economically viable polymeric products hitherto predominantly produced from oil-based synthetic polymers. However, the utilization of cellulose to its full potential is constrained by its recalcitrance to chemical processing. Both fundamental and applied aspects of cellulose dissolution remain active areas of research and include mechanistic studies on solvent–cellulose interactions, the development of novel solvents and/or solvent systems, the optimization of dissolution conditions, and the preparation of various cellulose-based materials. In this review, we build on existing knowledge on cellulose dissolution, including the structural characteristics of the polymer that are important for dissolution (molecular weight, crystallinity, and effect of hydrophobic interactions), and evaluate widely used non-derivatizing solvents (sodium hydroxide (NaOH)-based systems, N,N-dimethylacetamide (DMAc)/lithium chloride (LiCl), N-methylmorpholine-N-oxide (NMMO), and ionic liquids). We also cover the subsequent regeneration of cellulose solutions from these solvents into various architectures (fibers, films, membranes, beads, aerogels, and hydrogels) and review uses of these materials in specific applications, such as biomedical, sorption, and energy uses.