The aim of this work is to investigate the hydrogen-bonding interaction in poly(vinyl alcohol) (PVA)/poly(acrylic acid) (PAA) blending system and its influence on rheological properties in solution and the physical properties in solid state. Introducing PAA into PVA solutions resulted in a thickening behavior of blend solutions. The viscosity of the solutions increased with PAA content increasing, and a maximum viscosity could be obtained when the ratio of PVA/PAA was 70/30. The intermolecular hydrogen-bonding and miscibility between PVA and PAA in solid state were investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and mechanical measurements. The results displayed the great influence of introducing PAA on the properties of blending films. The tensile strength increased from 89.31 MPa to 119.8 MPa and Young’s modulus improved by over 300% with increasing PAA concentration compared with those of pure PVA films. By systematically studying the rheological behaviors of solutions and the physical properties of films, the influence of hydrogen-bonding in solutions and solid states were discussed.