Synthetic branched-chain glycolipids are suitable as model systems to understand biological cell membranes, particularly since certain natural lipids possess chain branching. Herein, four branched-chain glycopyranosides namely 2-hexyl-decyl-α-D-glucopyranoside (α-Glc-OC10C6), 2-hexyl-decyl-β-D-glucopyranoside (β-Glc-OC10C6), 2-hexyl-decyl-α-D-galactopyranoside (α-Gal-OC10C6) and 2-hexyl-decyl-β-D-galactopyranoside (β-Gal-OC10C6) with a total alkyl chain length of 16 carbon atoms have been synthesized and their phase behaviour studied. The partial binary phase diagrams of these non-ionic surfactants in water were investigated by optical polarizing microscopy (OPM) and small-angle X-ray scattering (SAXS). The introduction of chain branching in the hydrocarbon chain region is shown to result in the formation of inverse structures such as the inverse hexagonal and inverse bicontinuous cubic phases. Comparison of the four compounds showed that they exhibited different polymorphism, especially in the thermotropic state, due to contributions from anomeric and epimeric effects according to their stereochemistry. The neat compound of α-Glc-OC10C6 exhibited a lamellar (Lα) phase whereas dry α-Gal-OC10C6formed an inverse bicontinuous cubic Ia3d (QII(G)) phase. Both β-anomers of glucoside and galactoside adopted the inverse hexagonal phase (HII) in the dry state. Generally, in the presence of water, all four glycolipids formed inverse bicontinuous cubic Ia3d (QII(G)) and Pn3m (QII(D)) phases over a wide temperature and concentration range. The formation of inverse non-lamellar phases by these Guerbet branched-chain glycosides confirms their potential as materials for novel biotechnological applications such as drug-delivery and crystallization of membrane proteins.