To characterise the composition of sulphur-containing constituents in Chinese chive ( Allium tuberosum Rottler), GC–MS and HPLC analyses were carried out, using 12 varieties of Chinese origin, 4 varieties of Japanese origin and 6 commercially available cultivars. Five disulphides (dimethyl, allyl methyl, methyl 1-( E)-propenyl, diallyl, and allyl 1-( E)-propenyl), two trisulphides (dimethyl and allyl methyl), and two vinyldithiins (3-vinyl-[4 H]-1,2- and 2-vinyl-[4 H]-1,3-) were identified on the basis of their mass spectral and GC-retention data. Among the detected sulphur compounds, sulphides with a methyl group predominated over those with an allyl group. This was supported by the HPLC estimations, suggesting that all cultivars examined had much greater amounts of methiin than alliin. Also, two novel compounds were tentatively identified as [3 H,4 H]-1,2-dithiin and [2 H,4 H]-1,3-dithiin on the basis of their mass spectral features, GC-retention data, and some experimental results on their formation in reaction mixtures with different proportions of methiin and alliin. Their formation mechanism was proposed.