Ultra-high-resolution neutron diffraction studies of BiFe 0.8Co0.2O3 show a transition from a cycloidal space modulated spin structure at T = 10 K to a collinear G-type antiferromagnetic structure at T = 120 K. The model of antiparallel directions of Fe3+ and Co3+ magnetic moments at the shared Wyckoff position describes well the observed neutron diffraction intensities. On heating above RT, the crystal structure of BiFe0.8Co0.2O 3 changes from a rhombohedral R3c to a monoclinic Cm. At 573 K only the Cm phase is present. The collinear C-type antiferromagnetic structure is present in the Cm phase of BiFe0.8Co0.2O3 at RT after annealing. © 2013 American Chemical Society.