To trace the plasticizing effects of propylene glycol (PG) on poly(vinyl alcohol) (PVA), the rheological properties of PVA solutions in dimethyl sulfoxide (DMSO) and the physical properties of PVA films were discussed in terms of PG content. Both properties were closely related to the hydrogen bond breaking effects of PG The 6 and 12 wt% PVA solutions containing PG exhibited Bingham behavior, which was more noticeable at lower plasticizer content and higher polymer concentration. The 6 wt% PVA solutions containing more than 30 wt% PG showed a sudden decrease of viscosity over the frequency range of 0.08 and 0.2 rad/s. However, the 12 wt% PYA solutions showed no viscosity reduction even at a PG content up to 40 wt%. The glass transition temperature of the PVA/PG films was almost linearly decreased with increasing PG content but an abrupt reduction was observed at a plasticizer content 30 wt%, suggesting that the hydrogen bond breaking effects of PG on PVA became dominant between 20 and 30 wt%. This effect was further supported by the similar tendency of the tensile properties.