A series of blends of poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) were prepared by solution mixing and casting. Glycerol was used as plasticizer. The blends were characterized for their physicochemical and thermo-mechanical properties. The FTIR results revealed the molecular level interaction between PVA and PAA at all blend ratios. The incorporation of PAA significantly reduced the storage modulus of PVA at a given temperature. PVA gradually lost its crystalline character with the increase of PAA and became fully amorphous when the PAA content in the blend exceeded 50 wt%. The kinetic parameters of the semi-crystalline blends were determined using the Avarami-Erofeev model, which showed excellent fitting with the experimental data from DSC. The loss in crystallinity of PVA also contributed to an increase in swelling of the blend when the PAA content is increased. The morphology study by FE-SEM demonstrated that there is no phase separation among the blend components at all blend ratios.