Two new supramolecular compounds based on tungsten–vanadium polyoxoanions formulated as Cu(2,2′-bipy) 3 2H 14PW 2.2V 9.8O 40(VO) 2Cu(2,2′-bipy) 2H 2O 2PW 2.2V 9.8O 40(VO) 2·10H 2O ( 1) and Cu 4(2,2′-bipy) 4(H 2O) 2(PO 4) 2H 6.5PW 8.4V 3.6O 40·2H 2O ( 2) (2,2′-bipy=2,2′-bipyridine) have been synthesized hydrothermally and characterized by IR, TG, XPS and X-ray diffraction analyses. Crystal structure analyses reveal that compounds 1 and 2 exhibit novel 2D supramolecular layer structures constructed from tungsten–vanadium polyoxoanions and different types of secondary building units (SBUs), respectively, the different SBUs are formed by Cu(2,2′-bipy) 2H 2O 2+ and Cu(2,2′-bipy) 3 2+ cations in compound 1 and Cu 4(2,2′-bipy) 4(H 2O) 2(PO 4) 2 2+ cations in 2, respectively. Study of magnetic properties indicated the presence of antiferromagnetic behaviors for both compound 1 and 2. Two new supramolecular compounds were reported. Compounds 1 and 2 exhibit novel 2D supramolecular layer structures constructed from tungsten–vanadium polyoxoanions and different types of secondary building units, respectively.