The structures of cell-wall mannans isolated from Aphanoascus mephitalus, A. fulvescens, A. verrucosus, and A. reticulisporus have been investigated by chemical analyses and 1D and 2D 1H and 13C NMR techniques. It was found that all of them consists of a relatively simple comb-like structure of the disaccharide repeating block [-->6)-[alpha-Manp-(1-->2)]-alpha-Manp-(1-->]. The conformations around the alpha-(1-->2) and alpha-(1-->6) linkages in these kinds of polymers were also studied by using molecular mechanics and dynamics calculations, together with NOE data. The results are similar to those found within the oligosaccharide chains of glycoproteins, with a well-defined conformation for the alpha-(1-->2) linkage and a certain restriction around the alpha-(1-->6) bonding imposed by the 2-substitution.