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The reaction of secondary amines with CS under mild conditions using reduced graphene oxide (rGO) as a green catalyst was reported, which provided an efficient access to the one-pot synthesis of bis(aminothiocarbonyl)disulfides. The rGO can be recycled at least four times without any loss of catalytic activity. A plausible mechanism was proposed. Graphical Abstract: [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]