The synthesis of nine new surfactants with multiple hydroxyls on the headgroup is described in detail. Comparisons of the cmc values with chemical structures lead to useful generalizations (e.g. polyhydroxylation aids micellization owing, probably, to hydrogen bonding among the headgroups in the Stern region). None of the compounds, unfortunately, is able to induce oil/water (o/w) microemulsions in the absence of an additional cosurfactant; simple and generally useful three-component o/w microemulsions remain a worthy goal. An X-ray analysis reveals how one of the nine surfactants, with a large headgroup and short tail, packs in the solid state.