Tobacco constituents, such as cellulose, lignin and pectin were blended with appropriate level to make matrix mimicking the real tobacco constituents of Burley and flue-cured tobacco. The pyrolysis products of these matrices were determined by GC (HP 6890)/MS (HP 5973) after pyrolysis using Double-shot pyrolyzer (Frontier Lab.) at the temperature range from 300 °C to 800 °C with heating rate of 50 °C per minute. The profiles of pyrolysate were compared with the smoke components profiles of cigarettes that were made of Burley and flue-cured leaf, respectively. In the case of flue-cured mimicking matrix, more levoglucosan, D-gluconolactone, 1,6-anhydro-ß-D-glucofuranose and furfural type components were found in the pyrolysate than that of Burley mimicking. Na₂CO₃ and K₂CO₃ as combustion promoter, and 2 catalysts, Pt and Pd on alumina support, were pyrolysed with the matrix to inspect the effects of these potent ingredients on the process of pyrolysis. Salts did not affect the pyrolysis process but catalyst significantly did, so the profile of pyrolysate component was largely altered from the blank. The behavior of tobacco additives in smoking cigarette could be simulated by the pyrolyzer-GC/MSD method using the matrix mimicking the real tobacco leaf.