Based on the building block of 2-phenyl-4,6-di(pyridin-2-yl)pyrimidine(L = C20H14N4), a Cu(I) polymer [(Cu C20H14N4)(Cu Cl2)]∞ and a salt with H2SO4 [(C20H16N4)(HSO4)2] have been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction. In the Cu(I) polymer, although the central metal ions of Cu(I) directly coordinate with the building block L, they still do not assembly expected grid-type complexes and there exists a one-dimensional chain constructed through coordinate bonds. In the salt, hydrogen bonds along with two kinds of π···π supramoleuclar interactions fabricate two-dimensional(2D) networks which further generate a 3D supramolecular architecture via interlayer π···π interactions. Fluorescent spectra show that the L emits blue fluorescence and its Cu(I) polymer and salt decrease the fluorescent intensity. Based on the building block of 2-phenyl-4,6-di (pyridin-2-yl) pyrimidine (L = C20H14N4), a Cu (I) polymer [(Cu C20H14N4) (Cu Cl2)] ∞ and a salt with H2SO4 [(C20H16N4) (HSO4) 2] have been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction. Although the central metal ions of Cu (I) directly coordinate with the building block L, they still do not assemble expected grid-type complexes and there exists a one-dimensional chain constructed through coordinate bonds. In the salt, hydrogen bonds along with two kinds of π ... π supramoleuclar interactions fabricate two-dimensional (2D ) networks which further generate a 3D supramolecular architecture via an interlayer π · π interaction. Fluorescent spectra show that the L emits blue fluorescence and its Cu (I) polymer and salt decrease the fluorescent intensity.