A systematic structure variation of a classical amphiphile (dodecyl-beta-D-glucopyranoside) is performed, demonstrating the influence of anomeric linkage, configuration, ring size and flexibility as well as electric charges on the mesophase behaviour. In addition, we have investigated the thermotropic and lyotropic properties of some long chain alkyl glycosides with monosaccharide headgroups. The thermotropism was measured with polarizing microscopy and differential scanning calorimetry, and additionally the lyotropism with FTIR spectroscopy and X-ray diffraction.