A new sugar-derived Schiff's base ligand N-(3-tert-butyl-2-hydroxybenzylidene)-4,6-O-ethylidene-beta-D-glucopyran osylamine (H3L1) has been developed which afforded the coordinatively labile, alcoholophilic trinuclear Cu(II) complex [Cu-3(L-1)(2)(CH3OH)(H2O)] (1). Complex 1 has been further used in the synthesis of a series of alcohol-bound complexes with a common formula of [Cu-3(L-1)(2)(ROH)(2)] (R = Me (2), Et (3), Pr-n (4), Bu-n (5), (n)Oct (6)). X-ray structural analyses of complexes 2-6 revealed the collinearity of trinuclear copper(II) centers with Cu-Cu-Cu angles in the range of 166-172 degrees. The terminal and central coppers are bound with NO3 and O-4 atoms, respectively, and exhibit square-planar geometry. The trinuclear structures of 2-6 can be viewed as the two {Cu(L-1)}(-) fragments capture a copper(II) ion in the central position, which is further stabilized by a hydrogen-bonding interaction between the alcohol ligands and the sugar C-3 alkoxo group. Complex 2 exhibits a strong antiferromagnetic interaction between the Cu(II) ions (J = -238 cm(-1)). Diffusion of methanol into a solution of complex 1 in a chloroform/THF mixed solvent afforded the linear trinuclear complex [Cu-3(L-1)(2)(CH3OH)(2)(THF)(2)] (7). The basic structure of 7 is identical to complex 2; however, THF binding about the terminal coppers (CU-O-THF = 2.394(7) and 2.466(7) angstrom) has introduced the square-pyramidal geometry, indicating that the planar trinuclear complexes 2-6 are coordinatively unsaturated and the terminal metal sites are responsible for further ligations. In the venture of proton-transfer reactions, a successful proton transfer onto the saccharide C-3 alkoxo group has been achieved using 4,6-O-ethylidene-D-glucopyranose, resulting in the self-assembled tetranuclear complex, [Cu-4(HL1)(4)] (8), consisting of the mononuclear Cu(II) chiral building blocks, {Cu(HL1)}.