In this study, the tobacco extractives have been investigated by-using comprehensive two-dimensional gas chromatograpy/time-of-flight mass spectrometer (GCxGC/TOFMS). The different column systems were tested and compared, and the proper GCxGC/TOFMS conditions were suggested. Auto data processing of peak table provided by TOFMS software combined with manual identification was used to assign the components. About 1093 compounds with S/N≥ 100 were identified by using the developed method. Comparative analyses of the extractives from four commercially available tobacco grades (one is from Zimbabwe, three are from China) were performed, quantitative differences of 83 compounds (from the four grades) were found to be significant.