Reaction of NH4VO3 with sulfur dioxide affords the hexanuclear cluster (NH4)2(Et4N)[(V(IV)O)6(mu4-O)2(mu3-OH)2(mu3-SO3)4(H2O)2]Cl x H2O (1), and the decapentanuclear host-guest compound (Et4N)5{Cl subset [(VO)15(mu3-O)18(mu-O)3]} x 3 H2O (2). Sequential addition of magnesium oxide to an acidic aqueous solution of NH4VO3 (pH approximately 0) followed by (NH4)2SO3 resulted in the formation of either the non-oxo polymeric vanadium(IV) compound trans-(NH4)2[V(IV)(OH)2(mu-SO3)2] (3) or the polymeric oxovanadium(IV) sulfite (NH4)[V(IV)O(SO3)1.5(H2O)] x 2.5 H2O (4) at pH values of 6 and 4, respectively. The decameric vanadium(V) compound {Na4(mu-H2O)8(H2O)6}[Mg(H2O)6][V(V)10(O)8(mu6-O)2(mu3-O)14] x 3 H2O (5) was synthesised by treating an acidic aqueous solution of NH4VO3 with MgO and addition of NaOH to pH approximately 6. All the compounds were characterised by single-crystal X-ray structure analysis. The crystal structure of compound 1 revealed an unprecedented structural motif of a cubane unit [M4(mu4-O)2(mu3-OH)2] connected to two other metal atoms. Compound 3 comprises a rare example of a non-oxo vanadium(IV) species isolated from aqueous solution and in the presence of the reducing agent SO3(2-), while compound 4 represents a rare example of an open-framework species isolated at room temperature (20 degrees C). In addition to the synthesis and crystallographic studies, we report the IR and magnetic properties (for 1, 2 and 3) of these vanadium clusters as well as theoretical studies on compound 3.