A solid-phase micro-extraction (SPME) and gas chromatography/triple quadrupole mass spectrometry (GC/MS/MS) method was developed to analyze graftage-related black tea samples. Data extraction and statistical analysis were performed using Agilent MassHunter Profinder and Agilent Mass Profiler Professional (MPP) software. The characteristic volatile compounds, which were identified or tentatively identified, were subjected to principle component analysis and hierarchical clustering analysis to reveal the differences among tea samples.