An investigation of influence of cryogenic treatment on extremely dilute aqueous solution of poly(vinyl alcohol) (PVA) was performed by viscometry. The solution was frozen in liquid nitrogen or in a freezer at-25℃, then thawed at ambient temperature and concentrated by evacuation. The viscosity of the solution was measured using the dilute method. The experimental results indicated that the viscosity of the solution is related to N, the times of the freezing and thawing cycle, and the temperature for freezing. Undergoing a treatment of freezing and thawing, the viscosity of the solution is decreased, while it can be recovered the value of before the treatment as the solution had been heated at a high temperature. Thus, a conclusion may be obtained; that is, for an extremely dilute aqueous solution of PVA, which concentration is below Cgel, threshold concentration for gelation, an intramolecular hydrogen bonding cohesional entanglement can be formed by freezing as N>5. However, in the case of N<5, it not only formed an intramolecular hydrogen bonding but also produced an intermolecular hydrogen bonding. At the same time, the abnormal behavior of reduced viscosity of the solution in extremely dilute concentration region has been explained.