A method for ecstasy volatiles a??signaturea?? analysis based on two-dimensional gas chromatography separation and time-of-flight mass spectrometry detection (GC ?? GC-TOFMS) is presented. Organic impurity volatiles were extracted by head space solid phase microextraction (HS-SPME). The final column phase choice of the four different column combinations tested was a low-polarity 5 phenyl polysilphenylene-siloxane coupled with a polyethylene glycol phase, which best displayed the complex impurity profile. Second dimension (2D) retention time reproducibility was found to be about 1 RSD, and area reproducibility of SPME sampling was just over 5 RSD for compounds with S/N ratio of about 100.