Bacterial cellulose (BC) was mechanically fractured in vacuum at 77 K; this resulted in the scission of the beta-1,4 glycosidic linkages of BC. The chain-end-type radicals (mechanoradicals) generated from the scissions were assigned by electron spin resonance (ESR) spectral analyses. A diblock copolymer of BC and poly(methyl methacrylate) (BC-block-PMMA) was produced by the mechanical fracture of BC with MMA (methyl methacrylate) in vacuum at 77 K. Radical polymerization of MMA was initiated by the mechanoradicals located on the BC surface. The BC surface was fully covered with the PMMA chains of the BC-block-PMMA. Novel modification of the BC surface with the BC-block-PMMA was confirmed by spectral analyses of ESR, Fourier-transform infrared, H-1 NMR, and gel permeation chromatography.