Ferrihydrite is an important iron oxyhydroxide for earth and environmental sciences, biology, and technology. Nevertheless, its mineral structure remains a matter of debate. The stumbling block is whether a significant amount of tetrahedrally coordinated iron is present. Here we present the first X-ray magnetic circular dichroïsm (XMCD) measurements performed on a well characterized synthetic sample of 6-line ferrihydrite, at both K and L2,3energy edges of iron. XMCD results demonstrate unambiguously the presence of tetrahedrally coordinated Fe(III) in the mineral structure, in quantities compatible with the latest extended X-ray absorption fine structure (EXAFS) analyses suggesting a concentration of 20–30%. Moreover, we find an antiferromagnetic coupling between tetrahedral and octahedral sublattices, with the octahedral sublattice parallel to the external magnetic field.