Poly(N-vinyl-2-pyrrolidone) (PVP), a water-soluble polymer, is known for its excellent biocompatibility. It is generally recognized that the properties of polymers may be profoundly affected by the structure of water absorbed in them. In this study, Fourier transform infrared (FT-IR) in attenuated total reflection (ATR) and transmission mode was performed to examine the diffusion and structure of water in PVP and its copolymers. The obtained spectra were analyzed using two-dimensional (2D) IR with the aid of density functional theory (DFT) calculations. The 2D IR of time-resolved FT-IR/ATR spectra shows that type II water between 3300 and 3500 cm(-1) occurs earlier during the water absorption process, which is also demonstrated by transmission FT-IR at the initial stage of water absorption. Conversely, type II water changes last when desorption takes place. Results from DFT calculations indicate that type II water might be monomeric or dimeric water molecules interacting with a carbonyl group in the pyrrolidone moiety. Furthermore, it is found that vibrations less than 3300 cm(-1) (type I water) arise from water molecules involved in a carbonyl group interacting with more than two water molecules. It is reasonable that the transmission FT-IR spectra of film with an extra low water amount hardly show vibration bands below 3300 cm(-1); however, this region is distinct in the FT-IR/ATR spectra of fully swollen film. In addition, vibration bands between 3800 and 3500 cm(-1) (type III water) are assigned to free water or water with relatively weak hydrogen bonding, as supported by the transmission FT-IR spectra of polyacrylonitrile (PAN) and the calculation results. Therefore, the diffusion process and the structures of water in PVP and its copolymers can be successfully accessed on the basis of the 2D IR analysis and DFT calculations.