The geological disposal of high level radioactive waste requires careful budgeting of the heat load produced by radiogenic decay. Removal of high-heat generating radionuclides, such as 137Cs, reduces the heat load in the repository allowing the remaining high level waste to be packed closer together therefore reducing demand for repository space and the cost of the disposal of the remaining wastes. Hollandites have been proposed as a possible host matrix for the long-term disposal of Cs separated from HLW raffinate. The incorporation of Cs into the hollandite phase is aided by substitution of cations on the B-site of the hollandite structure, including iron. A range of Cs containing iron hollandites were synthesised via an alkoxide-nitrate route and the structural environment of Fe in the resultant material characterised by Mossbauer and X-ray Absorption Near Edge Spectroscopy. The results of spectroscopic analysis found that Fe was present as octahedrally co-ordinated Fe (III) in all cases and acts as an effective charge compensator over a wide solid solution range.