The structure of acidic fungal polysaccharides, isolated from the cell wall of Cylindrocladium and Calonectria species, has been investigated by chemical analysis, methylation and reductive cleavage analyses, and 1D and 2D 1H and 13C NMR spectroscopy. The polysaccharides have an idealized repeating unit: [formula: see text] linked to a small mannan core (< 5%), with n = 3 for Cylindrocladium penicilloides and C. quinqueseptatum and n = 5 for Calonectria theae, C. crotalariae, and C. colhounii.