Liquid-crystalline derivative of β-cyclodextrin (BCD) was prepared by covalent linking of monocholesteryl succinate (ChMS) with β-cyclodextrin. To the best of our knowledge, this was first ever attempt so far of its kind, in which BCD has been converted into its liquid-crystalline derivative through covalent linkage of a mesogen. The degree of substitution (DS) obtained was ≈2.00. The product was characterized by various techniques, such as FT-IR, NMR, DSC, hot-stage-coupled optical polarizing microscopy (OPM), microanalysis and chemical methods. Cholesterol-linked β-cyclodextrin (CDCh) derivative was found to exhibit thermotropic liquid-crystalline behavior. The product exhibited birefringence during first heating above 130°C, and it became isotropic at about 180°C, whereas the parent compound BCD decomposed without melting above 250 °C. A comparison of CDCh derivative to similar liquid-crystalline poly-saccharide derivatives is presented. © 2007 The Chemical Society of Japan.