Self-extinguishing multilayer coatings consisting of polyelectrolyte polyethylenimine (PEI) and ammonium polyphosphate (APP) have been constructed by the layer-by-layer assembly technique onto flexible and porous ramie fabric. Attenuated total reflection Fourier transform infrared spectroscopy and energy-dispersive X-ray analysis directly confirmed that PEI and APP were successfully incorporated onto the surface of ramie fabric sequentially. Assessment of the thermal and flammability properties for the coated ramie fabrics showed that the char residue at temperatures ranging from 400 to 600 degrees C during thermogravimetric analysis (TGA) and the self-extinguishing ability during vertical flame test were significantly enhanced as compared with the pristine sample, which showed strong dependency on the number of deposited layers, especially on the concentration collocation of both polyelectrolytes. This work provided a simple but effective