The red flour beetle,Tribolium castaneum(Herbst) (Coleoptera: Tenebrionidae), is a major storage pest that could lead to a wide range of damage. Its secretions have a significant impact on the quality of stored grain and food, leading to serious food safety problems such as grain spoilage and food carcinogenesis. This study investigates new detection techniques for grain storage pests to improve grain insect detection in China. The primary volatile organic chemicals (VOCs) in these secretions are identified using headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS). The specific VOCs that are unique toT. castaneumare selected as criteria for determining the presence ofT. castaneumin the granary. To obtain more specific VOCs, experiments were designed for the analysis ofT. castaneumsamples under different extraction times, two types of SPME fibers and two GC-MS devices of different manufacturers. The experimental results showed that 12 VOCs were detected at relatively high levels, seven of which were common and which were not detected in other grains and grain insects. The seven compounds are 1-pentadecene, 2-methyl-p-benzoquinone, 2-ethyl-p-benzoquinone, 1-hexadecene, cis-9-tetradecen-1-ol, m-cresol and paeonol. These seven compounds can be used as volatile markers to identify the presence ofT. castaneum, which could serve as a research foundation for the creation of new techniques forT. castaneummonitoring.