AbstractMetal complexes of thiophosphorylated cellulose, when heated, give rise to high char yields. These and related observations suggest that such derivatisation may give rise to novel flame retardant treatments for cellulosic materials.The kinetics of thermal degradation of cellulose, cellulose ethylthiophosphate (CESP) and metal complexes of the CESP have been studied by thermogravimetry (TG) and differential thermal analysis (DTA) from ambient temperature to 700°C in dynamic air to investigate the potential flame retardance of the CESP and its metal complexes. Various parameters such as energy, entropy, enthalpy and free energy of activation have been calculated using the Broido method and transition state theory. For the decomposition stage of thermal degradation, the activation energies of the CESP samples lie in the range 53‐133 kJmol−1and of the metal complexes, 108‐177kJmol−1, which are found to be lower than that of cellulose (187 kJmol−1). Scanning electron micrographs of the CESP show that the fibrillar structure of cotton has become more evident and chars retain the general morphology of the original fibre although severe, localised zones of damage reflect the gross chemical and physical changes occurring during pyrolysis. The IR spectra of chars of modified samples indicate formation of compounds containing C=O, C=C and P=O groups. The mechanisms of thermal degradation of the CESP and its metal complexes have bee