The present study aims at the development and validation of a quali-quantitative headspace solid-phase microextraction gas chromatography–mass spectrometry (HS-SPME GC-MS) method for the analysis of odorants in different Chinese and Japanese green teas. A 65 µm PDMS/DVB fiber was used, and GC-MS was performed on a ZB-5 (30 m × 0.25 mm ID, 0.25 μm film) column. The main odorants in green tea samples were identified and the method was fully validated. Linearity (r2 0.981–0.999), sensitivity (LOQ 0.005–0.04 µg/mL), reproducibility (CV% 3.12–10.37), accuracy (recovery% 79.08–99.17) and matrix effect (ME% −9.5 to +4.5) were determined. Quantitation of 2,4-heptadienal, β-damascenone, β-ionone, linalool, indole, 2-ethyl-6-methyl-pyrazine, 2-ethyl-5-methyl-pyrazine, 2-ethyl-3,6-dimethylpirazine, 2-ethyl-3,5-dimethyl-pyrazine and 2-acetyl-pyrazine was carried out in the presence of isotopically labeled compounds as the internal standards. The proposed method was applied to the comparison of the profile of the volatile flavor compounds (VFCs) of green tea subjected to roasting treatment at three different temperatures (160, 180 and 200 °C for 30 min). In particular, the roasting process was monitored by following the quantitative variations of the selected odorant content, considered as the most important contributory components to the Hojicha or black tea (roasted tea) flavor. A temperature of 160 °C was found to be the best roasting temperature.