Strategies for modelling the EXAFS of a range of compounds with structural features common to the diiron subsite of the [FeFe] hydrogenase H-centre are compared, and this has allowed identification of highly constrained models that still permit expression of the main structural characteristics of the compounds. Despite giving self-consistent values of the iron–scatterer distances, the EXAFS analysis fails to give unambiguous identification of the stereochemistry and composition of the compounds, and this necessitates the integration of results obtained using other spectroscopic and computational approaches. The combination of infrared spectroscopy, EXAFS, and ab initio DFT calculations are shown to provide a particularly potent approach for the study of metal carbonyl compounds of this class. In this case the EXAFS-derived iron–scatterer distances provide the basis of the starting point for DFT geometry optimization calculations, and the final distances together with the calculated infrared spectrum provides a means of validating the computed geometry. The approach is applied both to compounds of known structure and to the examination of the unstable products of chemical or electrochemical reduction.