Some unusual ionic conducting phenomena were observed from ion-containing microemulsion membranes. Contrary to conventional wisdom, it was found that under the same ionic concentration, large ions exhibit higher mobilities than smaller ones. They are possibly explained by the existence of hydration shells, which eventually made the lighter cations larger. This is further supported by the sharp conductivity drop when the system was cooled below the freezing point of water. In addition, conductivity drop at higher ionic concentration was also observed.