The smoke suppression of rigid polyurethane foam (RPUF) modified by melamine was investigated based on three sections: the condensed phase, the carbon layer, and the gas phase. In the condensed phase, the results of thermogravimetry, X-ray photoelectron spectroscopy (XPS) N1S spectrum, and Fourier transform infrared spectroscopy indicated that melamine could suppress the degradation of RPUF by reacting with the aromatic hydrocarbons. It also reduced the smoke generation because the volatilizable aromatic hydrocarbons were the principal smoke precursors in a fire. In the carbon layer, the decrease from 38.50% to 24.76% of the inner layer oxygen content identified by XPS full-spectrum and C1S spectrum indicated that melamine could prevent oxygen from transferring into the inner foam by the formation of an enhanced surface carbon layer, and the enhanced carbon layer could also block the release of smoke precursors. In the gas phase, the content of total aromatic hydrocarbons declined to 59.12% according to pyrolysis gaseous chromatography mass spectroscopy and indicated that melamine could reduce the smoke precursors. The results of smoke density chamber and cone calorimeter tests revealed that the addition of the melamine could decrease the smoke density of burning RPUF. Copyright © 2014 John Wiley & Sons, Ltd.