We synthesised glycosyl diacylglycerols bearing unsaturated or chiral methyl branched fatty acid chains. The thermotropism was measured with polarising microscopy and additionally the lyotropism with the contact preparation method. The synthesised compounds displayed thermotropic SA (lamellar), cubic and columnar phases and investigation of the lyotropic phase behaviour led to the observation of inverted bicontinuous cubic VII phases, lamellar Lα phases and normal bicontinuous cubic VI phases. The phases are discussed with respect to the chemical structures that have been varied systematically to derive structure–property relationships.