The microstructure of smokes from afterburning (at temperatures of ~ 700-800°С) of charcoal is analyzed. It is shown that the smoke particle size spectrum at afterburning of charcoal is noticeably different from smokes from thermal decomposition of resinous wood samples. The results of inversion of data of the polarization nephelometer have shown that, in spite of high temperature of decomposition and free oxygen access to the thermal decomposition chamber, the optical properties of the formed smoke are determined by finely dispersed particles with r ≈ 0.03-0.35 µm and the complex refractive index m ≈ 1.590 - 0.011i. The obtained estimations of the complex refractive index show a low content of the absorbing component (soot particles) as opposed to the usual smokes from burning. The volumetric concentration of medium-size particles in the range 0.35 < r < 0.7 µm is negligibly small. The specificity of characteristics of optical and microphysical aerosols in this case is connected with a low content of complex organic compounds and resinous components in the structure of the burnt samples (charcoal).