Ammonia/ammonium thiocyanate (NH3/NH4SCN) is an excellent swelling agent and solvent for cellulose, even at a high degree of polymerization. Because polymorphic conversion in cellulose has been a long-standing, perplexing, troublesome problem, we have undertaken to study that mechanism. Solid state CP/MAS C-13-NMR and X-ray analysis proved to be very useful analytical techniques for the task. It appears that during temperature cycling, specific cellulosic inter- and intramolecular hydrogen-bonds are broken as polymorphic conversion proceeds sequentially from the polymorph I to II to III, and finally at total solvation to amorphous. This proceeds correspondingly via transformation of the polymorph conformations of CH2OH from trans-gauche, "tg," to gauche-trans, "gt," to gauche-gauche, "gg."