Molecular dynamics (MD) simulations of three polysulfones (poly(ether sulfone) PESU, poly(phenylene sulfone) PPSU and polysulfone PSU) in dry and hydrated states were undertaken in order to study the specific interactions between water and glassy polymer matrices of the same structural family. Dry polysulfone models were generated using a hybrid pivot Monte Carlo-MD single-chain sampling technique and the resulting relaxed densities were found to be in close agreement with experimental data. Hydrated systems are found to reproduce quite well volumetric changes experimentally observed. The concentrations of sulfonic groups can explain qualitatively their different water solubilities. Water is preferentially hydrogen-bonded to two sites which either link two polymer sites, or one polymer site and another water, or two other waters. A detailed analysis of these water bridges that are formed is presented. Only a small quantity of potential bridging sites are occupied for water contents near the experimental saturation. The free fractional volumes, the probe accessible volumes, the swelling of the polymers, the water-polymer interactions and the hydrogen bond lifetimes, are also presented for these polysulfones. Water-water interactions and water clusters are found to be more important in the more hydrophilic PESU in comparison to the less hydrophilic PSU. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 2312-2336, 2010