Two new supramolecular compounds based on tungsten–vanadium polyoxoanions formulated as [Cu(2,2′-bipy) 3 ] 2 H 14 [PW 2.2 V 9.8 O 40 (VO) 2 [Cu(2,2′-bipy) 2 H 2 O] 2 ][PW 2.2 V 9.8 O 40 (VO) 2 ]·10H 2 O (1) and [Cu 4 (2,2′-bipy) 4 (H 2 O) 2 (PO 4 ) 2 ]H 6.5 [PW 8.4 V 3.6 O 40 ]·2H 2 O (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) 2 H 2 O] 2+ and [Cu(2,2′-bipy) 3 ] 2+ cations in compound 1 and [Cu 4 (2,2′-bipy) 4 (H 2 O) 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.