AbstractSolid‐state 13C‐NMR spectroscopy was used to characterize native cellulose pellicles from two strains of Gluconacetobacter xylinus (ATCC 53582, ATCC 23769), which had been statically cultivated in Hestrin–Schramm (HS) medium containing fully 13C‐labeled β‐D‐glucose‐U‐13C6 as the sole source of carbon. For both samples, the 13C‐NMR chemical shifts were completely assigned for each 13C‐labeled site of cellulose Iα with the aid of 2D refocused INADEQUATE NMR. To determine the principal chemical shift tensor components, a pulse sequence based on the recoupling of anisotropy information (RAI) was applied at 10 kHz MAS. The detailed 13C tensors of cellulose Iα from different bacterial celluloses are thus available now for the first time, and these results have been compared with previously published data of nonenriched material and with theoretical predictions. Copyright © 2008 John Wiley & Sons, Ltd.