Two new Schiff base compounds, tailed by the fluoroalkoxy, were synthesized in a three-step process. Those supramolecular structures constructed by hydrogen bonding show good liquid crystal properties with higher clear points and wider mesomorphic phase ranges than other analogs containing a terminal alkoxy chain. Investigation of the optical textures by polarizing microscopy reveals that terminal fluorinated substituents convert the nematic phase of supramolecular hydrogen-bonding complexes with terminal alkoxy chains into the smectic A phase of those with terminal fluoroalkoxy chains.Graphical abstractTwo new schiff base compounds, with fluoroalkoxy as the terminal chains, were synthesized in three steps. Their supramolecular hydrogen bonding complexes show smectic A phase with higher clear points and wider mesomorphic phase ranges than those of the analogs with a terminal alkoxy chain.Highlights► We synthesized new schiff base with fluoroalkoxy as the terminal chains. ► The corresponding supramolecular liquid crystals show good mesomorphic properties. ► Wide mesomorphic phase ranges and high order were found. ► The corresponding supramolecular liquid crystals show smectic A phase. ► However, the analogs with alkoxy terminal chains show nematic phase.