Cyclotriveratrylene (CTV) has attracted much attention because of its good chemical stability, small cavity, stable conformation, and facile modification. In this article, two water-soluble CTV derivatives (CTV-G and CTV-L) functionalized by glucose and lactose residues were synthesized, respectively. Unexpectedly, sugar-bearing CTVs exhibit a distinct photoluminescence, which might be ascribed to the enhanced planar conformation of cyclotriveratrylene ring derived from the spatial effect of bulky branch groups. The interaction between the water-soluble CTV derivatives and C(60) was investigated in organic solvent and aqueous solution, which was further characterized by fluorescence spectra, ultraviolet-visible spectra, and Raman spectra. CTV-G can associate with C(60) to form supramolecular complex with 1:1 molar ratio (K(a) = 1.38 × 10(5) M(-1), 298 K). As for CTV-L, a similar complex with a lower association constant (K(a) = 5.09 × 10(4) M(-1), 298 K) can also be formed.