The crystal and magnetic structures of orthorhombic ε-Fe 2O3 have been studied by simultaneous Rietveld refinement of X-ray and neutron powder-diffraction data in combination with Mössbauer spectroscopy, as well as magnetization and heat-capacity measurements. It has been found that above 150 K, the ε-Fe2O3 polymorph is a collinear ferrimagnet with magnetic moments directed along the a axis, whereas the magnetic ordering below 80 K is characterized by a square-wave incommensurate structure. The transformation between these two states is a second-order phase transition and involves subtle structural changes mostly affecting the coordination of the tetrahedral and one of the octahedral Fe sites. The temperature dependence of the ε-Fe2O3 magnetic properties is discussed in light of these results. © 2006 American Chemical Society.