New coordination polymers of copper(II) and copper(I), [Cu(tfa)2(pyz)2]n(Htfa = trifluoroacetic acid, pyz = pyrazine) (1), [Cu2(tfa)2(CH3O)2-(pyz)2]n(2), and [Cu2(tfa)2(pyz)3]n(3), have been synthesized and characterized structurally. The crystal structure of2consists of methoxo-bridged dinuclear copper(II) units which are connected by pyrazine molecules to form a two-dimensional network. The crystal structure of3shows a two-dimensional net-like structure, where each copper(I) atom has a distorted tetrahedral arrangement. The magnetic property of2is antiferromagnetic.