We use surface-specific heterodyne-detected vibrational sum-frequency generation spectroscopy (HD-VSFG) and surface tension measurements to investigate the molecular structure of the surface of aqueous solutions of polyvinyl alcohol (PVA) polymers with average molecular weights of 10000 g/mol and 125000 g/mol. We find that the interfacial water molecules have a preferred orientation with their hydrogen-bonded O-H groups pointing away from the bulk, for both PVA10000 and PVA125000. This observation is explained from the ongoing hydrolysis of the acetyl impurities on the PVA polymer chains. This hydrolysis yields negatively charged acetate ions that have a relatively high surface propensity. For both PVA10000 and PVA125000 the strong positive signal vanishes when the pH is decreased, due to the neutralization of the acetate ions. For solutions with a high concentration of PVA10000 the interfacial water signal becomes very small, indicating that the surface gets completely covered with a disordered PVA polymer film. In contrast, for high concentrations of PVA125000 the strong positive water signal persists at high pH, which shows that the water surface does not get completely covered. The HD-VSFG data combined with surface tension data indicate that concentrated PVA125000 solutions form a structured surface layer with pores containing a high density of interfacial water.