Two-dimensional (2D) correlation ATR-FTIR spectroscopy was used to study the dynamic diffusion behavior and state of water in syndiotactic polypropylene (S-PP). The 2D asynchronous spectra of water bending band clearly reveal that there are three separate bands in the 1800-1500cm-1 region. These three bands at 1676, 1645, and 1592cm-1 are assigned, respectively, to the aggregated water with strong hydrogen bond, the aggregated water with moderate strong hydrogen bond, and the "free water". On the basis of this approach, the following mechanism for the diffusion process of water in S-PP has been proposed: the aggregated water molecules first diffuse into the polymer during the diffusion process. The water molecules with strong hydrogen bond will diffuse slower than water with moderate strong hydrogen bond because of their large size. In the late stage of the diffusion process, some aggregated water molecules in the PP matrix are forced to dissolve into the "free water" form.