•Skatole, sclareololide and sclareololide were first identified in Laoshan tea.•Co-eluted compounds (furfural, cis-linalool oxide) were separating by GC × GC-qMS.•The interactions exist among aroma compounds in tea samples. To investigate the key aroma compounds in Laoshan green teas (Huangshan (S1), Changling (S2), and Fangling (S3)), gas chromatography-mass spectrometry-olfactometry (GC-MS-O), a flame photometric detector (FPD), odor activity value (OAV), and comprehensive two-dimensional gas chromatography mass spectrometry (GC × GC-qMS) were employed. A total of 50 aroma compounds were perceived and 24 compounds were identified as important compounds related to OAV, such as dimethyl sulfide (OAV: 126–146), skatole (OAV: 27–50), furaneol (OAV: 8–27), (Z)-jasmone (OAV: 16–23), 2-methylbutanal (OAV: 15–22), and 3-methylbutanal (OAV: 68–87). Furthermore, the S-curve method was used to research the effect of aroma compounds on the threshold of aroma recombination (AR). The AR thresholds decreased from 3.8 mL to 0.45, 0.66, 0.93, 0.95, 0.75, 1.09, 3.01, and 2.57 mL after addition of eight compounds (skatole, furaneol, (Z)-jasmone, α-damascenone, sclareololide, dihydroactinidiolide, vanillin, and δ-valerolactone), indicating that those compounds (OAV >1) were contributors to the overall aroma of Laoshan teas.