The Michael addition reaction of a series of alkyl vinyl sulfoxides (CH2˭CH-SO-R; R = CH3(MVSO), C2H5(EVSO), t-C4H9(BVSO)) with poly(vinyl alcohol) (PVA) was carried out after investigating the model reaction with isopropyl alcohol. The addition reaction was found to proceed in the presence of sodium hydroxide as catalyst. This sulfinylation of PVA proceeded more easily with MVSO and EVSO than with BVSO, and a polymer containing up to 60 mol% sulfoxide unit was obtained with MVSO and EVSO. The solution viscosity as well as the solubility behavior of the modified PVA' having various types and contents of sulfoxide group were also examined.