A series of symmetrical bolaamphiphiles possessing a diphenylbutadiene core and glucopyranoside head groups linked together by oligomethylene spacers, were synthesized and their thermotropic liquid crystalline properties investigated by polarized light optical microscopy, differential scanning calorimetry, X-ray diffraction and electro-optic switching. In spite of the presence of chiral centers, amphiphilic sugars in general do not exhibit macroscopic chirality and this phenomenon is attributed to strong hydrogen bonding between sugar head groups resulting in microphase-segregated layer like arrangements. In the present study all the molecules investigated exhibited the smectic C* phase, i.e., tilted lamellar phase with macroscopic chiral ordering of the molecules. The stability of this phase increased with increase in the length of the oligomethylene spacers. Whereas for derivatives with spacers containing ≤4 methylene groups, the smectic C* phase was observed only in the cooling phase, for those containing spacers with ≥5 methylene groups this phase was observed both in the heating and cooling cycles. The absorption and fluorescence spectra of these materials suggest that the unusual observation of macroscopic chirality in these bolaamphiphiles containing free hydroxyl groups could be attributed to self-aggregating behavior of the diphenylbutadiene core.