A new procedure is proposed for the sampling and storage of hydrogen sulphide (H2S) and volatile thiols (methanethiol or methyl mercaptan, ethanethiol and propanethiol) for their determination by liquid chromatography. The sampling procedure is based on the trapping/pre-concentration of the analytes in alkaline aqueous solution containing an organic mercurial probe p-hydroxymercurybenzoate, HO-Hg-C6H4-COO- (PHMB), where they are derivatized to stable PHMB complexes based on mercury-sulfur covalent bonds. PHMB complexes are separated on a C18 reverse phase column, allowing their determination by liquid chromatography coupled with sequential non-selective UV-vis (DAD) and mercury specific (chemical vapor generation atomic fluorescence spectrometry, CVGAFS) on-line detectors. PHMB complexes, S(PHMB)2CH3S-PHMB, C2H5S-PHMB and C3H7S-PHMB, are stable alt least for 12 h at room temperature and for 3 months if stored frozen (-20 degrees C). The best analytical figures of merits in the optimized conditions were obtained by CVGAFS detection, with detection limits (LODc) of 9.7 microg L(-1) for H2S, 13.7 microg L(-1) for CH(3)SH, 17.7 microg L(-1) for C2H5SH and 21.7 microg L(-1) for C3H7SH in the trapping solution in form of RS-PHMB complexes, the relative standard deviation (R.S.D.) ranging between 1.0 and 1.5%, and a linear dynamic range (LDR) between 10 and 9700 microg L(-1). Conventional UV absorbance detectors tuned at 254 nm can be employed as well with comparable R.S.D. and LDR, but with LODc one order of magnitude higher than AFS detector and lower specificity. The sampling procedure followed by LC-DAD-CVGAFS analysis has been validated, as example, for H2S determination by a certified gas permeation tube as a source of 3.071+/-0.154 microg min(-1) of H2S, giving a recovery of 99.8+/-7% and it has been applied to the determination of sulfur compounds in real gas samples (biogas and the air of a plant for fractional distillation of crude oil).