In the current study, a new approach to the synthesis of highly destacked ReS2 layers embedded in amorphous carbon via the thermal decomposition of a tetraoctylammonium perrhenate precursor, under sulfidizing atmosphere (15% v/v H2S mixture H2S/H2 gas), is described. X-ray diffraction, scanning electron microscopy, scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy analysis of the thermolysis product confirm the formation of rhenium disulfide. The synthesized compound is found as single layers with a minor proportion of few-layer arrangements, embedded in amorphous carbon. X-ray diffraction, UV–visible diffuse reflectance, and thermogravimetry analysis were made in order to characterize the metal-organic salt precursor, showing that the perrhenate ions are dispersed widely from each other in the matrix of the organic cations, forming an inorganic-organic salt. The special arrangement of these ReS2 layers has a potential use as a heterogeneous catalyst due to the high proportion of edge sites. •Highly destacked ReS2 layers embedded in amorphous carbon were synthesized.•The novel synthesis involved the sulfidization of an (Oct4N)ReO4 precursor.•Amorphous carbon act as a structural stabilizer in the final composite.