Huge quantities of sulphur are yielded as by‐products in the oil and gas industry. Disposal raises a relevant environmental issue. Sulfanes, H2Sn (n > 2), could be the ideal molecular form for sulphur disposal. They are up to 99% wt. made of sulphur and being liquid can be pumped into geological structures, even at room temperature. Since sulfanes can be synthesized only at low yield (<1%) by direct reaction between H2S and sulphur, we investigated a new amine‐catalyzed synthesis. Using aliphatic long‐chained amines as catalysts, it is possible to obtain sulfanes by direct H2S and sulphur reaction in almost quantitative yield. Structures of the sulfanes formed during this new reaction were studied by GC‐MS, LC‐MS and 1H NMR, to investigate the nature of the complexes formed between amine and sulfane. © 2010 American Institute of Chemical Engineers Environ Prog, 2010