Two new hybrid vanadium arsenates (2,2′-bpy) 2 (V V O 2 ) 2 (AsO 4 )⋅H 3 O⋅H 2 O 1 and (2,2′-bpy) 2 V 4 O 7 (HAsO 4 ) 2 2 (2,2′-bpy=2,2′-bipyridine) were synthesized under hydrothermal reaction conditions and structurally characterized by single-crystal X-ray diffraction, thermogravimetric analysis (TGA), IR, powder XRD and elemental analyses. Crystal data for 1: monoclinic, C2/c, a=13.867(7) Å, b=22.351(10) Å, c=9.252(4) Å, β=103.857(4)°, V=2784(2) Å3, Z=4. Crystal data for 2: triclinic, P-1, a=8.4401(1) Å, b=9.3309(11) Å, c=9.6996(10) Å, α=96.910(4)°, β=110.860(2)°, γ=98.595(4)°, V=693.23(11) Å3, Z=1. Compound 1 is composed of discrete {(VO 2 ) 2 (AsO 4 )} 3-membered rings bonded to two 2,2′-bpy ligands. Compound 2 exhibits a 2D arsenic vanadate network decorated with 2,2′-bpy ligands.