V. Acinetobacter baumannii produces a variety of capsular polysaccharides (CPS) via genes located at the chromosomal K locus and some KL gene clusters include genes for the synthesis of specific sugars. The structures of K11 and K83 CPS produced by isolates LUH5545 and LUH5538, which carry related KL11a and KL83 gene clusters, respectively, were established by sugar analysis and one- and two-dimensional1H and13C NMR spectroscopy. Both CPS contain L-rhamnose (L-Rha) and 6-deoxy-L-talose (L-6dTal), and both KL gene clusters include genes for dTDP-L-Rhap synthesis and a tle (talose epimerase) gene encoding an epimerase that converts dTDP-L-Rhap to dTDP-L-6dTalp. The K11 and K83 repeat units are the same pentasaccharide, consisting of D-glucose, L-Rha, L-6dTal, and N-acetyl-D-glucosamine, except that L-6dTal is 2-O-acetylated in K83. However, the K units are linked differently, with L-Rha in the main chain in K11, but as a side-branch in K83. KL11 and KL83 encode unrelated Wzy polymerases that link the K units together and different acetyltransferases, though only Atr8 from KL83 is active. The substrate specificity of each Wzy polymerase was assigned, and the functions of all glycosyltransferases were predicted. The CPS structures produced by three closely related K loci, KL29, KL105 and KL106, were also predicted.