New coordination polymers of copper(II) and copper(I), [Cu(tfa)(2)(pyz)(2)](n) (Htfa = trifluoroacetic acid, pyz = pyrazine) (1), [Cu-2(tfa)(2)(CH3O)(2)-(pyz)(2)](n) (2), and [Cu-2(tfa)(2)(Pyz)(3)](n) (3), have been synthesized and characterized structurally. The crystal structure of 2 consists of methoxo-bridged dinuclear copper(II) units which are connected by pyrazine molecules to form a two-dimensional network. The crystal structure of 3 shows a two-dimensional net-like structure, where each copper(I) atom has a distorted tetrahedral arrangement. The magnetic property of 2 is antiferromagnetic.