Novel ionizable polymer networks were prepared from oligo(ethylene glycol) (OEG) multiacrylates and acrylic acid (AA), employing bulk radical photopolymerization techniques. The properties of these materials exhibited a complex dependence on the network structure and composition. Penetrant sorption experiments demonstrated that the crosslinked structure of the copolymers depended very strongly on the AA content as well as the number of ethylene glycol groups. The impact of varying the AA content and the oligo(ethylene glycol) chain length on the polymer chain dynamics was examined using diffusion and C-13 NMR relaxation studies. The penetrant uptake studies indicated a coupling of Fickian and relaxation-driven contributions to the swelling behavior. The effect of increasing the AA content on the characteristic chain relaxation time was reversed as the oligo(ethylene glycol) chain length was varied, indicating that chain relaxation is controlled by structural considerations, for shorter oligo(ethylene glycol) chains, and by compositional considerations, for longer oligo(ethylene glycol) chains. Measured compositional effects on solid state 13C NMR relaxation times supported these conclusions.