UV irradiation of 2-, 3-, or 4-pyridylacrylic acid (2-, 3-, and 4-HPYA) with (CuCl)-Cl-1 at 230 nm in 4 N HCl for 1 week and subsequent hydrothermal reactions yielded three novel highly stable 3-D copper(I)-olefin dimers, [(2-H(2)PYA)(2)Cu2-+Cl4](n) (1), [(3-H(2)PYA)(2)Cu2+Cl4](n) (2), and [(4-H(2)PYA)(2)Cu2+Cl4(I)](n) (3), respectively, in which H-bonds play a key role in the stabilization of supramolecular Cu(I)-olefin system and thus the formation of the 3-D networks. The electrochemical properties of 1-3 are also reported.