Complex ring (13)C resonance lines of the cross-polarization/magic angle spinning (CP/MAS) (13)C NMR spectra of cellulose triacetate (CTA) I and CTA II were completely assigned, for the first time, by (13)C-enriched CTA allomorphs. The (13)C-enriched CTA I was prepared by heterogeneous acetylation of bacterial cellulose which was biosynthesized by Acetobacter xylinum (A. xylinum) ATCC10245 from culture medium containing D-(2-(13)C)-, D-(3-(13)C)-, or D-(5-(13)C)glucose as a carbon source, while CTA II samples were obtained by solution acetylation of the (13)C-enriched bacterial celluloses. From comparison of the spectra of normal CTA prepared from ramie with those of the enriched CTA samples, it was revealed that all carbons composed of CTA I appeared as a singlet, while those of CTA II except for C1 were shown as equal-intensity doublets in the CP/MAS (13)C NMR spectrum. This finding suggests that CTA I is made up of one kind of glucopyranose residue while there are two magnetically inequivalent sites in the unit cell of CTA II in the same population.