A novel technique in membrane separation based on the phenomenon of electroosmosis, recently developed by us [Jain et al., J. Membrane Sci., 78 (1993) 53] has been used to demonstrate the practicability of the phenomenon for the separation of 1,4-dioxane from a dioxane-water mixture The method shows favourable prospects as a membrane separation process, at least for the separation of close boiling mixtures, provided that the components of the mixture possess a large difference in their dielectric constant values. The analysis of the data indicates that the separation of dioxane increases as the dioxane concentration in the feed solution increases. It is also found that the separation of dioxane increases as the applied electrical potential difference across the membrane increases.