Solution-state NMR, requiring close to isotropic mobility in solution, has traditionally been challanging for technical celluloses and often chemically modified cellulosics. While chemically modified cellulosics are often soluble in molecular solvents, those materials that include blocks of unmodified chains are typically not mobile enough in solution to afford sufficient relaxation times to allow for rapid equilibration and high resolution analysis. Recent developments in chemically stable direct-dissolution electrolytes (Fliri et al. 2003) has allowed for high-quality dissolution of a wide range of crystalline celluloses to sufficient concentrations for high-resolution and signal-to-noise NMR analysis. This abstract will illustrate the utility of this method and its application to typical samples that significantly benefit from the chemical resolution afforded. Examples include regioselective chemical modification of nanocelluloses and cellooligomers, as highly promising materials where defined regiochemistry is critical.