Bicontinuous microemulsions are investigated as a model system for thespecific adsorption phenomena of metal ions at the water–oil interface. Mixingan extremely hydrophobic ion extractant – tributyl phosphate (TBP) used hereas co-surfactant- with an extremely hydrophilic sugar-based surfactant, wedescribe a new type of functionalized microemulsions that shows the classicalWinsor phases, by varying the surfactant/extractant ratio. We focus on theWinsor III-type microemulsions by determining the phase diagrams whereas themicrostructures were accessed by performing small angle neutron scatteringexperiments. Ultimately, these microemulsions may pave the way for the designof new selective ion extraction processes.