Radiant syngas cooler (RSC) is the key heat recovery equipment in coal gasification system. The syngas from gasifier carries large amount of slags in which the mass fraction of fly ash less than 100 μm is about 20%. Studying the optical properties of fly ash has high significance for the optimization of heat transfer calculation in RSC. A new experimental method was proposed to inversely calculate the radiative parameters of particles—“KBr transmittance-reflectance method”. By measuring the “directional-hemispherical” reflectance and transmittance of fly ash particles by FTIR under the wavelength range of 0.55 - 1.65 μm, using the four-flux model to solve the radiative transfer equation and combing with Mie theory, the absorption and scattering efficiency of 22.7 μm fly ash and optical constant (also known as complex refractive index, m = n + ik) of fly ash were inversely calculated. The results indicated that for fly ash with large size parameter, there was no obvious change of the absorption and scattering efficiency when the mass fraction of Fe₂O₃ was between 5.65% and 16.53%, which was well explained by Mie theory; The obtained optical constant was close to the results of KBr trans-mittance method.