Instant tea powder is an important processed product of tea. Previous studies have reported in-depth investigations regarding the processing technology used for instant tea powder, however, only few studies are available on the quality of instant tea powder. The volatile components of instant oolong tea powder were analyzed using gas chromatography-mass spectrometry (GC-MS) combined with solid-phase micro-extraction (SPME). The results showed that the optimal SPME conditions included using the 50/30-μm Divinylbenzene-Carboxen-Polydimethylsiloxane DVB-CAR-PDMS adsorption fiber at 70℃ for 40 min. GC-MS analysis identified 39 volatile components, consisting mainly of linalool, trans-ocimene, cis-linalool oxide, and trans-linalool oxide, at concentrations of 16422.8, 3407.8, 2549.7, and 2163.1 μg/kg, respectively. Based on the analysis of odor activity value (OAV), the compounds mainly contributing to the aroma and their corresponding odor activity values were: linalool, 2,737,138; cis-linalool oxide, 360,522; trans-linalool oxide, 424,950; trans-β-ocimene, 56,796; and benzene acetaldehyde, 31,708. The above results together indicated that the main volatile components and aroma contributors were linalool, trans-β-ocimene, cis-linalool oxide, and trans-linalool oxide. These results provide reference data for the evaluation of the volatile components contributing to the aroma quality of instant oolong tea powder.