The comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry was applied to analyze the volatiles of Artemisia argyi leaves extract. 210 components were detected and 65 compounds were identified with high similarity. Most of them were terpenes and their oxygenated derivatives. The pyrolysis of the Artemisia argyi leaves extract was investigated with TG-DSC and pyrolysis apparatus. TG curve showed that the main weight loss occurred between 145～643℃, among which the volatiles lost at 145～465℃ and complex pyrolysis occurred at 465～643℃. The pyrolysis products of different temperatures were identified. The results showed that most of the volatiles including terpenes, alcohols and aliphatic hydrocarbons were directly transferred via distilling. Flavoring substances (furans) as well as harmful compounds (carbonyl compounds, naphthalene, indene) were generated at the pyrolysis zone of 600～900℃.