Oligomeric cellulose with an average degree of polymerization of 7.68 and a polydispersity of 1.04 has been fractionated using solution processes. Three fractions have been obtained through initial dissolution, subsequent crystallization, and solvent precipitation, respectively. The resulting oligocellulose fraction has an average degree of polymerization of 7.70 and a polydispersity of 1.01, respectively. Cellulose IV2 crystals form in the oligocellulose fraction, and reversibly transform to II and back to IV using simple solvents.