The complexes [Ph 4As] 2[V 2O 3(NO 3) 6], 1 and [Ph 4As] 2[V 2O 3Cl 4(NO 3) 2], 2, crystallise from solution in the reaction of tetraphenylarsonium nitrate with VO(NO 3) 3 and VOCl 3, respectively. The compounds were characterised by their IR and Raman spectra and single crystal X-ray analysis. Compound 1 crystallises in the triclinic space group P 1, a = 9.580(1), b = 10.782(2), c = 13.631(2) A ̊ , Z = 1 and R = 0.059, whilst 2 crystallises in the monoclinic space group P2 1/c, a = 10.176(1), b = 17.691(2), c = 13.955(2), Z = 2 and R = 0.034. The crystal structures show that the dianions are related, the vanadium atoms in both species possess distorted octahedral symmetry, this being achieved by one terminal and one bridging oxygen atom, one bidentate nitrate group and four other monodentate ligands. An unusual feature of 1 is the presence of both monodentate and bidentate modes of nitrate coordination whilst 2 is the first example of a mixed halonitrato species of vanadium(V) to be isolated.