The stinkbug's volatile compositions would alter very much before and after stinkbugs were disturbed or irritated, which caused the alarming effect. An efficient headspace solid-phase microextraction sampling method was established to study the alarming volatile characteristics and potential alarming volatiles of stinkbugs (Tessaratoma papillosa) followed by gas chromatography-mass spectrometry detection. The number of volatiles identified was 16 and 22 before and after stinkbug irritation, respectively. Long-chain alkanes, alkenes, and alcohols consisted of the main volatile compositions of Tessaratoma papillosa. When stinkbugs were disturbed, the typical unsaturated volatiles were released, especially including a series of tridecane derivatives. In comparison with the volatile compounds of lichi leaf and flower (plants the stinkbug eats), it could be seen that most stinkbug alarming volatiles were synthesized by the insects themselves, and that they do not originate from their food. The different statistical alarming volatile characteristics of Tessaratoma papillosa before and after irritation were interpreted by principal component analysis in the original Chromatography Data Processing System. However, temperature and light did not affect the alarming volatile characteristics. The variety of the stinkbug alarming volatile characteristics before and after irritation was specified by common model strategy. Tridecane, [E]-2-hexenal, dodecane, [E]-2-hexen-1-ol acetate, and 2,3-dimethyl-1-pentene contributed most to the various alarming volatile characteristics before and after irritation, which might be the potential alarming volatiles. It is hoped that this work will provide useful information for insect control.