The magnetic structure of two natural samples of goethite (α-FeOOH) with varying crystallinity was analyzed at 15 and 300 K by neutron diffraction. The well crystallized sample has thePb′nmcolor space group and remained antiferromagnetic up to 300 K, with spins aligned parallel to thecaxis. The purely magnetic 100 peak, identifying this color space group, was clearly resolved. The nanocrystalline sample shows a phase transition to the paramagnetic state at a temperature below 300 K. This lowering of the Néel temperature may be explained by the interaction of magnetic clusters within particles. The nuclear structure, refined with the Rietveld and pair distribution function methods, is consistent with reports in the literature.