Oxovanadium clusters are interesting both as models of bulk magnets and in their own right. Results are presented suggesting that in Na-6[H6V12O30F2].22H(2)O (see Figure) it is meaningful to decide which particular vanadium centers should be considered as 5+ and which as 4+. It is shown that in principle it is possible to tune and design the topology, and thus the magnetic properties, of polyoxovanadates(IV/V) by means of the template effect.