A new catalytic system for enantioselective [2+ 2]-cycloaddition reaction of 2- methoxycarbonyl-2-cyclopenten-1-one with thioacetylene derivatives is described. The use of a catalytic amount (20–30mol%) of copper (II) salt with chiral bis-pyridine ligand was found to be effective in promoting the [2+ 2]-cycloaddition reaction, furnishing the corresponding bicyclic compound in good yield and good enantioselectivity.