In this work, the deconstruction mechanism of corn stover cell wall polymers during ball milling was evaluated. The characterization showed that ball milling not only brought about the dissociation of the cross-linked cellulose-hemicellulose-lignin complex but also led to the depolymerization of the cell-wall polymers especially the carbohydrates. Micromorphology characterization revealed that mechanical treatment disrupted the orderly fibrillar matrices with a porous structure. The breakage of β-1,4 glycosidic bonds in cellulose and the decomposition of arabinoxylans indicated the modification in polysaccharide chains. The degradation of lignin-carbohydrate complex (LCC) linkages and the cleavage of β-O-4′ linkages in lignin approved the partial degradation of lignin. In conclusion, mechanochemistry is an efficient force to make the polymers in plant fibers more digestible.