The structural and physical effects of partially substituting Cd for Fe in goethite have been investigated. The solubility of Cd2+ in goethite is ~10 mol.%, i.e. Fe0.905Cd0.095OOH. The structures of the substituted goethites have been refined, using the Rietveld method, from synchrotron X-ray powder diffraction data. There is a progressive increase in the size of the unit-cell parameters and unit-cell volume, upon the incorporation of much larger Cd2+ ion (0.95 Å) compared with Fe3+ (0.645 Å) in the goethite structure, together with a reduction in crystallinity. Transmission electron microscopy measurements confirm the crystallite size decreases as the Cd2+ content increases in goethite structure.