Star-shaped molecules consisting of a 1,3,4-oxadiazole core derivatized with alkoxy-substituted phenyl ethynylenes, FD12 (dodecyl) and FD16 (hexadecyl) were synthesized. These molecules exhibited enantiotropic columnar mesophases over a wide temperature range, with the liquid crystalline phases exhibiting strong blue fluorescence. On cooling, FD12 transformed into a transparent glass at room temperature wherein the liquid crystalline texture was retained. The glassy film remained stable over a period of one year and exhibited blue luminescence with an absolute quantum yield of 26%. The oxadiazole derivatives formed stable luminescent gels in decane and study of their morphology by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) indicated formation of interlocked network of self-assembled fibers. X-ray diffraction (XRD) analysis of the xerogel of these derivatives indicated oblique columnar ordering of the molecules within the fibers. The length of the alkyl substituent was observed to have a significant effect on the absorption and fluorescence properties of the gels, which was attributable to the role of the alkyl substituents in controlling the nature of the molecular packing within the self -assembled fibers of the gels.