Routes towards the formation of inverted opal vanadium oxide electrodes are presented. Different methods of template infiltration using an IPA diluted solution of vanadium triisopropoxide are discussed and the resulting morphologies investigated using scanning electron microscopy. The effect of different heat treatments and method of sphere removal on morphology and structure is also considered. Solvent template removal retains the hydrolysed amorphous V2O5 structure. Raman scattering spectroscopy identifies the degree of V2O5 crystallinity that results from the different heat treatments. For a thicker inverted opal formed using a polystyrene template as opposed to a monolayer PMMA template, under similar conditions a different phase of vanadium oxide is observed evident by variations in Raman scattering response.