A horonic-acid-appended amphiphile bearing an azobenzene chroniophore in the chain center (3) was synthesized. Although 3 could not form the membrane-like, ordered aggregate by itself, it formed a phase-separated aggregate in a dipalmitoylphosphatidylcholine (DPPC) matrix membrane. When saccharides were added, the boronic acid group reversibly formed the saccharide complexes, and 3 in the DPPC matrix membrane became CD-active with the appearance of exciton-coupling bands. Comparison of the saccharide absolute configuration with the CD intensity established that the saccharide possessing the OH group (as 3-OH, 4-OH, and 5-CH2OH) in the same side as the cis-1,2-diol gives the strong CD band. Judging from the structure of 3-saccharide complexes, these "same-side" OH groups can enjoy intermolecular hydrogen-bonding interactions, which eventually induce the chiral orientation of azobenzene chromophores. This is a novel membrane system useful to read oui the information stored in the saccharide structure and to create novel membrane structures by added saccharides.