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An organic–inorganic hybrid CuII–ErIII heterometallic arsenotungstate Na3[Cu(en)2(H2O)][Cu(en)2]1.5[H3Er(α-AsW11O39)2]·4H2O (1) (en = ethylenediamine) has been hydrothermally synthesized and structurally characterized by elemental analyses, IR and UV spectra, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry and single-crystal X-ray diffraction. 1 displays an organic–inorganic 2-D sheet structure constructed by sandwich-type [H3Er(α-AsW11O39)2]8− fragments and [Cu(en)2]2+ connectors. From the topological viewpoint, if the [H3Er(α-AsW11O39)2]8− fragments are viewed as 3-connected nodes and [Cu(en)2]2+ connectors are considered as linkers, the 2-D sheet can be simplified into a 2-D (6,3)-network topology. Keywords: Polyoxometalate, Arsenotungstate, CuII–ErIII heterometallic derivative, Spectroscopic characterization