In this contribution, we review and critically compare the results of the analyses we have previously performed on water sorption thermodynamics in a series of polyimides. The experimental investigation was performed by combining gravimetric tests and in situ vibrational spectroscopy. A non-equilibrium theory, based on a compressible lattice framework accounting for the glassy state of the polymer and for the occurrence of hydrogen bonding interactions, has been used to interpret data. Information at a molecular level gained by vibrational spectroscopy has been used to tailor the model equations. The main features of water sorption thermodynamics are well captured, qualitatively and quantitatively, by the adopted model which displays a remarkable agreement with experimental results.