The structure of a polysaccharide from the red seaweed, Porphyra capensis, growing along the coast of Namibia and South Africa was investigated. Algae growing at different sites and collected at different times gave a polysaccharide extract with similar chemical components. FTIR and NMR spectral analysis showed that the polysaccharide from P. capensis had a typical porphyran structure. It has the linear backbone of alternating 3-linked β-d-galactose and 4-linked α-l-galactose-6-sulfate or 3,6-anhydro-α-l-galactose units. The ratio of α-l-galactose-6-sulfate and the 3,6-anhydrogalactose is 1.2:1, as reflected by a 1 H NMR spectrum. A high degree of methylation occurred at the C-6 position of the d-galactose units. The degree of methylation was 0.64 for the d-galactose residues.