We report a systematic FTIR study of the perturbation of water "sorbed" into the polymers PET and PVC as a function of crystallinity (PET) or plasticizer content (PVC). Band shapes of the composite v(OH) band of H2O obtained by the ATR technique have been fitted to individual components,corresponding to those recently found for pure water itself. A detailed quantitative analysis of the frequency shifts and relative intensties has led to conclusion that these component bands show direct evidence for the breaking of the water network in the polymer matrix and that this process depends on the polymer chemical and/or physical properties, Evidence is also found for interactions of water with the polymer at the lower end of the hydrogen bond interaction scale. The component band relative intensities (compared with those of pure water) have been used to compute an intensity enhancement parameter, P, which is a measure of the perturbation of a particular water distribution due to dissolution in the polymer matrix. For PET, P varies systematically with density, reflecting the ability of water to penetrate the polymer microstructure. For PVC the plasticizer content (and hence T-g) has considerable influence on the sorption (and swelling) process and on the equilibrium content and state of water. Thus, ATR-FTIR has been used for the first time to demonstrate, via intensity enhancement, the extent of electronic perturbation at a polymer/water interface.