An atom economical and transition-metal and iodine free procedure of graphene oxide (a heterogeneous, recyclable, inexpensive, and environment-friendly carbocatalyst) mediated thiolation of indoles, using thiols as a thiolating reagent, has been developed. This methodology provides a catalyst-recyclable and organic-solvent-free protocol to afford 3-sulfenylindoles with good functional group tolerance and broad substrate scope.