The self-assembly phenomena on a special class of poly-hydroxy sugar surfactant have been studied extensively. This class of material is classified as amphitropic liquid crystals since they exhibit both thermotropic and lyotropic liquid crystalline properties. Hence the potential applications of these non-ionic surfactants are more versatile than those from the conventional lyotropic liquid crystals including those from thermotropic phases, but the latters are yet to be realized. Unfortunately, due to the lack of interest (or even awareness), fundamental studies in thermotropic glycolipids are scanty to support application development, and any tangible progress is often mired by the complexity of the sugar stereochemistry. However, some applications may be pursued from these materials by taking the advantage of the sugar chirality and the tilted structure of the lipid organization which implies ferroelectric behavior. Here, we present our studies on the stereochemical diversity of the sugar units in glycosides that form the thermotropic/lyotropic phases. The structure to property relationship compares different chain designs and other popular polyhydroxy compounds, such as monooleins and alkylpolyglucosides. Different structural properties of these glycosides are discussed with respect to their self-assembly organization and potential applications, such as delivery systems and membrane mimetic study.