CO2‐selective cross‐linked poly (ethylene oxide) (PEO) membranes were prepared by the UV irradiation of high molecular weight PEO in the presence of benzophenone as photo‐initiator, which act as a hydrogen‐abstracting agent. The main goal was to study the effects of the cross‐linking process on the structural properties of hydrogel films intended for the gas separation applications. It was found that the gel fraction, and cross‐link density enhanced, and the crystallinity, and the size of spherulites decreased by the cross‐linking process. Moreover, the permeation performances for N2, O2, CH4, and CO2 and the relationship between the gas permeation performances and physical properties were investigated. The results indicated that the degree of cross‐linking and crystallinity could be controlled by changing the initiator concentration, as by increasing the initiator content, the crystallinity percent and gas permeability of the membranes decreased, and the gas pair ideal selectivity of CO2/N2, CO2/CH4, CH4/N2, and O2/N2 increased.