In order to improve our understanding of how the goethite crystal structure is affected by the incorporation of metals (and by variations in the amount of the incorporation), and to review any possible synergistic and antagonistic effects of co-metals, the present investigation focused on the incorporation of multiple (di-, tri-, and tetra-) metals, i.e. Cr, Zn, Cd, and Pb, in the goethite crystallographic structure. A series of single- and multi-metal M-Cr/Zn/Cd/Pb-substituted goethites with M/(M+Fe) molar ratios = 0.10 were prepared. The general sequence of metal entry in single-metal substituted goethites was Zn = Cr > Cd > Pb and in multi-metal-substituted goethites was Zn > Cr ≥ Cd > Pb. Simultaneous incorporation of Cr, Zn, Cd, and Pb up to 10.5 mole % was achieved in goethite. Synchrotron X-ray diffraction and extended X-ray absorption fine structure (EXAFS) techniques were employed to assess the structural characteristics of the synthesis products. Rietveld refinement of XRD data showed small changes in unit-cell parameters and Fe/M–Fe/M distances due to M substitution(s). A typical goethite-like crystalline structure remained intact, however. The unit-cell parameters were mutually, linearly correlated, though Fe/M–Fe/M distances were not, indicating that complex changes occurred at the local scale. In single-metal substituted goethites, incorporation of Cr reduced the unit-cell volume by 0.13% while that of Zn, Cd, and Pb increased it by 1.09, 3.58, and 0.56%, respectively. The changes in multi-metal-substituted goethites appeared to be the complex combination of that of the individually incorporated metals. The X-ray absorption near edge structure study of Pb-substituted goethites showed that the majority of associated Pb was Pb2+, while Pb4+ was preferred over Pb2+ in the bulk structure. Measurements by EXAFS at the Fe K-edge indicated that the Fe polyhedra contracted in the presence of Cd2+ and Pb2+, providing room for the substitution of larger cations. Measurements by EXAFS at the Cr and Cd K-edges indicated symmetric Cr/Cd polyhedra with single Cr/Cd–O distances and, at Fe and Zn K-edges and the Pb LIII-edge, indicated asymmetric polyhedra with two sets of Fe/Zn/Pb–O distances. The Zn octahedra were possibly Zn(OH)4O2, which enlarged the metal–metal corner-sharing distance to 3.86 Å. This configuration of ligands around the Zn2+ cation might occur to balance local charges. Symmetric polyhedra appeared to reduce steric strains in the structure, compared to the asymmetric polyhedra. The result was that Cr enhanced the incorporation of Zn, Cd, and Pb, while the converse was true for Zn.