Ordered mesostructured hexagonal, cubic and lamellar vanadium-phosphorus-oxide phases displaying improved thermal stability, desirable bulk compositions, and vanadium oxidation states (3.8-4.3) for the partial oxidation of lower alkanes were synthesized using cationic (alkyl trimethyl ammonium salts), anionic (alkyl sulfonates and phosphates) and primary alkylamines as structure-directing agents. It was found that hexagonal mesophases were favored at short carbon chain lengths (C 1 2 -C 1 6 ), while cubic phases were favored for longer chains (C 1 8 ). Structure-directing agents were removed by calcination or Soxhlet extraction in ethanol. When structure-directing agents were removed by extraction, phase transformations from hexagonal to cubic to lamellar structures were observed. The improved thermal stability of these mesophases was attributed to the acidic self-assembly conditions in the vicinity of the isoelectric point of V(V) oxocations.