Abstract: Two new arsenic–vanadium clusters, [Zn(2,2′-bpy)3]2[As8V14O42(H2O)]·4H2O (1, 2,2′-bpy =2,2′-bipyridine) and [Zn(2,2′-bpy)(dien)]2[As8V14O42(H2O)]·2H2O (2, dien=diethylenetriamine), have been hydrothermally synthesized and characterized by IR, elemental analysis, EPR, XRD, TGA, magnetic measurements, and single-crystal X-ray diffraction analysis. Crystal data: 1, triclinic,, a=14.3793(2)Å, b=16.7706(2)Å, c=24.7077(1)Å, α=93.740(1)°, β=93.182(1)°, γ=113.363(1)°, Z=2; 2 orthorhombic, P4(3)2(1)2, a=21.3442(7)Å, b=21.3442(7)Å, c=15.8837(7)Å, Z=4. X-ray crystallographic study showed that compound 1 is composed of the discrete [As8V14O42(H2O)]4- polyoxoanions and chiral [Zn(2,2′-bpy)3]2+ cations, while compound 2 is constructed from [As8V14O42(H2O)]4− cluster anions and novel [Zn(2,2′-bpy)(dien)]2+ complex fragments linked through hydrogen bonds into a network. Variable temperature susceptibility measurements demonstrate the presence of antiferromagnetic interaction between VIV cations in 1 and 2. [Copyright &y& Elsevier]