<p dir="ltr">This study explores the flame retardancy of extracellular polymeric substances (EPS) derived from activated and blended sludges. A comprehensive set of experiments, including the extraction process, thermal measurement, and gas analysis, is conducted to investigate the possible flame-retardant mechanisms of the biomaterials in both condensed and gas phases. Both EPS-based biomaterials effectively form a char layer and release non-flammable gases, thereby slowing fire propagation. In particular, the EPS recovered from activated sludge demonstrate superior flame-retardant properties compared to their counterparts due to the higher activation energy, increased char residue content, and release of nitrogen-containing compounds during combustion.</p>