Regenerated cellulose was prepared from microcrystalline cellulose (MCC) via dissolution in three well-known nonderivatizing systems: ferric chloride/sodium tartarate/sodium hydroxide (FeTNa), sodium hydroxide/thiourea (NaOH/thiourea), and N-methylmorpholine-N-oxide (NMMO) systems. The effect of regeneration using the different systems on the supramolecular structure of the regenerated celluloses was studied using X-ray diffraction and Fourier transform infrared (FTIR). The effect of regeneration on supermolecular structure, morphology, and thermal stability of regenerated celluloses were studied using scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The effect of regeneration systems used on the chemical reactivity of cellulose toward carboxymethylation, acetylation, and cyanoethylation reactions was briefly studied. The results showed dependence of all the aforementioned properties on the dissolution reagent used in spite of that all studied reagents cause the same change in cellulose crystalline structure (from cellulose I to cellulose II). The degree of polymerization, crystallinity, and thermal stability of the regenerated cellulose (RC) samples were in the following order: NaOH/thiourea RC > FeTNa RC > NMMO RC. SEM micrograph showed unique surface for the NMMO RC sample. The reactivity of the different regenerated cellulose samples toward carboxymethylation, cyanoethylation, and acetylation depended mainly on the reaction system and conditions used rather than on crystallinity of regenerated cellulose. (C) 2008 Wiley Periodicals, Inc.