The structural and magnetic evolution in copper ferrite (CuFe2O4) caused by high-energy ball milling are investigated by x-ray diffraction, Mössbauer spectroscopy, and magnetization measurements. Initially, the milling process reduces the average grain size of CuFe2O4 to about 6 nm and induces cation redistribution between A and B sites. These nanometer-sized particles show superparamagnetic relaxation effects at room temperature. It is found that the magnetization is not saturated even with an applied field of 9 T, possibly as the result of spin canting in the partially inverted CuFe2O4. The canted spin configuration is also suggested by the observed reduction in magnetization of particles in the blocked state. Upon increasing the milling time, nanometer-sized CuFe2O4 particles decompose, forming alpha-Fe2O3 and other phases, causing a further decrease of magnetization. After a milling time of 98 h, alpha-Fe2O3 is reduced to Fe3O4, and magnetization increases accordingly to the higher saturation magnetization value of magnetite. Three sequential processes during high-energy ball milling are established: (a) the synthesis of partially inverted CuFe2O4 particles with a noncollinear spin structure, (b) the decomposition of the starting CuFe2O4 onto several related Fe–Cu–O phases, and (c) the reduction of alpha-Fe2O3 to Fe3O4. ©1998 American Institute of Physics.