Materials other than polymers, e.g. ceramic silicates, are currently being investigated for gas separation processes. The permeation characteristics of one such material, Vycor (Corning Glass #1370), have been reported for the separation of hydrogen from hydrogen iodide. This paper will describe the electron microscopy techniques applied to reveal the porous microstructure of a Vycor membrane. The application of these techniques has led to an increased understanding in the relationship between the substructure and the gas transport properties of this material.