Synthetic routes for the formation of opal assemblies as templates for the inverted opal vanadium oxide electrodes are presented. A method for the formation of monolayer opal templates on gold substrates is discussed and the formation of multilayer opal templates on conductive substrates by electrophoretic deposition is also described, with order defined by angle resolved light scattering measurements. Inverted opals are formed from a diluted solution of IPA and vanadium alkoxide precursor, infiltrated into the templates by several methods. The effect of different heat treatments and method of polymer template removal on the resulting inverse opal morphology and structure is investigated.