Acute fatal poisoning due to the inhalation of toxic gas frequently occurs in China. Volatile sulphur compounds (VSCs) are toxic to humans. In fatal poisoning investigations, such as those in industrial settings, a number of VSCs, including methanethiol (MT), dimethyl sulphide (DMS), dimethyl disulphide (DMDS) and dimethyl trisulphide (DMTS), can coexist. To date, there is limited data regarding these compounds in post-mortem cases. In the present study, we report toxicological findings in a fatal accident case with two victims. Headspace gas chromatography/flame ionization detector with two columns of different polarities was utilized to screen MT, DMS, DMDS and DMTS in blood. The limits of detection in both methods were 0.05 mg/mL. No sulphur compounds were detected in the blood samples of the two victims. DMS and DMDS were detected in the lungs at concentrations of 0.5 and 1.3 mg/g and 2.2 and 4.1 mg/g, respectively. DMDS liver concentrations were 2.5 and 6.5 mg/g. In addition to hydrogen sulphide, screening for additional VSCs could help establish the cause of death.