The crystal-chemical mechanisms by which transition metals are associated with goethite are fundamental to our understanding of the solubility and bioavailability of micronutrients and heavy metals in soils, and in the formation of laterite ore deposits. Transition metals such as Cr, Mn and Ni may sorb onto goethite by forming surface precipitates, surface complexes or by replacing Fe3+ in the goethite structure. In the work reported here, we investigated the local coordination environment of Cr, Mn and Ni in synthetic goethite using EXAFS spectroscopy. We demonstrate the isomorphous substitution for Fe3+ by Cr3+ (up to 8 mol.%), Mn3+ (up to 15 mol.%) and Ni2+ (up to 5 mol.%). We find, however, that the next-nearest-neighbour coordination environment changes with composition. The perturbations are likely to be responsible for limiting the accommodation of Cr3+, Mn3+ or Ni2+ in the FeOOH structure.