A multi-technique approach, incorporating nuclear magnetic resonance (NMR), elemental analysis, differential scanning calorimetry (DSC), thermogravimetric analysis and surface-area determination, has been used to investigate the formation of chars by oxidized cellulose. It was found that oxidation of the cellulose tends to increase the surface area of the resulting char. NMR, elemental analysis and DSC show how cellulose oxidation tends to increase aromaticity and cross-linking. This, in turn, decreases diffusion rates of volatiles out of the oxidized cellulose during pyrolysis, giving denser carbons and higher BET surface areas.