A casting process has been studied for charged polymers: the sulfonated polyimide ionomer membrane. The formation of the membrane has been followed by X-ray reflectivity as a function of temperature. The effect of equivalent weight has been also investigated. The thickness loss presents two regimes: the first one is linear vs time indicating that the models developed for noncharged polymer may be suitable for ionomers in the early period of drying. The second one corresponds to the loss of X-ray reflectivity signal. Moreover, the X-ray reflectivity signal seems to be correlated to the characteristic time of the sample drying. In complement, we have studied the influence of casting on the properties of the dried ionomer membranes. The transport coefficients of N(CH3)(4)(+) ions confined in two kinds of membranes that were differently cast were measured. The results show that shearing the ionomer solution during casting may lead to an enhancement of the anisotropy of structure and of transport. Moreover, we have studied the effect of both interfaces on the ion transport properties through the dried membranes.