The quality of jasmine tea is related to the volatiles of its infusion. In this study, the volatiles of jasmine tea infusion were extracted under the optimal conditions with a 50/30 μm DVB/CAR/PDMS fiber, tea/water ratio of 1:25 and extraction time of 5 min. A total of 204 volatiles were analyzed by comprehensive two-dimensional gas chromatography-quadrupole time-of-flight mass spectrometry (GC × GC-Q-TOF-MS). Twenty-five compounds were identified as the key volatile compounds by fold change (FC), orthogonal partial least squares discriminant analysis (OPLS-DA), and two-way orthogonal partial least squares analysis (O2PLS). Then optimal amount of flowers (80%–120%) was obtained by the equation describing key volatiles and quality of jasmine tea infusion. And 80% amount of flowers was more appropriate considering the production cost and more pleasant taste. This study laid a foundation for the extraction and research of volatiles of tea infusion and guided the reasonable amount of flowers to produce jasmine tea.