Prolonged high-intensity grinding can modify the crystal structure of solid substances and/or induce chemical reaction, which is referred to as mechanochemical reaction. Such reactions can exert positive influences on hydrometallurgical processes, therefore, many researchers have applied mechanochemical reactions for metals dissolution from minerals. The mechanism of mechanochemical reaction has been investigated using solid analyses and simulations. Structural changes caused by mechanochemical reactions are not yet sufficiently clarified because the ground samples are amorphous. The objective of this study was to analyze structural changes of cerianite in weathered residual rare earth ore by mechanochemical reduction. The ore was ground by planetary ball milling for 10, 60 and 720 min. Structural change was analyzed by the X-ray absorption near-edge structure and extended x-ray absorption fine structure analysis at the cerium L_III- and K-edges. These analyses revealed that the structural change of cerianite in this ore induced by mechanochemical reduction involved oxygen vacancy production. The process of the oxygen vacancy formation was closely coupled with the quantum effect of localization–delocalization of the 4f electron of cerium.