Poly(ethylene oxide) (PEO) networks prepared from the photopolymerization of bisphenol A ethoxylate diacrylate (BPA-EDA) have been investigated as a function of crosslinker molecular weight and copolymer composition. Dynamic mechanical and dielectric methods have been used to elucidate the thermal relaxation characteristics of the polymers as a function of network composition and architecture, and these properties were related to measured gas transport for CO2 separations. Copolymerization strategies involving the insertion of flexible PEG side chains along the network backbone proved effective in enhancing network free volume and increasing permeability. The gas transport performance of rubbery amorphous membranes based on the n = 15 BPA-EDA crosslinker (i.e., crosslinker encompassing 30 ethylene oxide repeat units between crosslinks) compared favorably to model polymers synthesized from poly(ethylene glycol) diacrylate. (C) 2008 Elsevier Ltd. All rights reserved.