Two new compounds based on As^III–V^IV polyoxometalates, [HAs₆V₁₅O₄₂(H₂O)][Cu(enMe)₂]_2.5·2H₂O (1), [H₂enMe]₂[As₈V₁₄O₄₂(H₂O)]·3H₂O (2), have been hydrothermally synthesized and characterized by IR, UV-vis, ESR, XPS spectra, elemental analyses, magnetic susceptibility studies and single-crystal X-ray diffraction analyses, respectively. X-Ray crystallographic studies reveal that 1 represents the first example of 2D structure constructed from [HAs₆V₁₅O₄₂(H₂O)]⁵⁻ anions and transition metal coordination complexes, in addition, it exhibits the first brick-wall-like 2D layer structure constructed from polyoxometalates and transition metal coordination complexes. 2 exhibits a very interesting stacking mode. The study of magnetic susceptibilities demonstrates the presence of antiferromagnetic interactions in both 1 and 2.