Two series of novel synthesized hexacatenars,O/nandM/n, containing two thiophene-cyanostilbene units interconnected by central fluorene units (fluorenone or dicyanovinyl fluorene) using a donor–acceptor–acceptor–donor (A–D–A–D–A) rigid core, with three alkoxy chains at each end, can self-assemble into hexagonal columnar mesophases with wide liquid crystal (LC) ranges and aggregate into organogels with flowerlike and helical cylinder morphologies, as revealed via POM, DSC, XRD and SEM investigation. Furthermore, these compounds were observed to emit yellow luminescence in both solution and solid states which can be adopted to manufacture a light-emitting liquid crystal display (LE-LCD) by doping with commercially available nematic LC.