Bis-[methyl-1-hydroxy-1-cyclopentene-2-dithiocarboxylate-O,S]nickel(II) 1 was prepared starting from methyl 2-hydroxycyclopent-1-encarbodithioate ligand (CPDT) and Ni(II), and catena-[( 2 -4,4 -Bipyril)-bis-(methyl-2-hydroxy-1-cyclopentene-2-dithiocarboxylate-O,S)]nickel(ΙΙ) 2 was prepared in good yields from 1 plus 4,4 -bipyridyl (bpy) by shish-kebab methodology. The structure of 1 was confirmed by FTIR, elemental analysis, 1 H NMR, UV-vis in chloroform solution and in solid, XPS, and PXRD. Compound 2 was characterized by FTIR, elemental analysis, UV-vis in chloroform solution, and in solid, XPS, PXRD, ESR, and solid state magnetization measurements. The structure of the polymer was established mostly by PXRD, ESR, and magnetization.