Superheating alcohol solutions of simple trimetallic vanadium(III) precursors gives the octa- and decametallic vanadium(III) clusters [V(8)(OEt)(8)(OH)(4)(O(2)CPh)(12)] (1) and [V(10)(OMe)(20)(O(2)CMe)(10)] (2). Cluster 2 is the largest vanadium(III) cluster synthesised to date. Thus solvothermal synthetic techniques are an excellent route to high-nuclearity vanadium(III) clusters. Both 1 and 2 consist of a planar or near-planar array of V(III) ions. The metal ions in 1 are bridged by either a micro(2)-hydroxide and two micro(2)-benzoate groups or two micro(2)-ethoxides and a micro(2)-benzoate groups, the two bridging arrangements alternating around the ring. In 2 each pair of neighbouring metal ions is bridged by two micro(2)-methoxides and a micro(2)-acetate, and this molecule is the V(III) analogue of Lippard's famous "ferric wheel". Preliminary magnetic susceptibility studies show the exchange coupling in both complexes to be antiferromagnetic in nature, with the coupling stronger in 1 than in 2.