A new type of ligand-free Ni-nanoparticles supported on rGO (size distribution average d = 9 ± 3 nm) is prepared and fully characterized via morphological (Fe-SEM), structural (P-XRD, HR-TEM) and spectroscopic (ICP-EOS, XPS) analysis tools. The metal composite was effectively employed in the unprecedented heterogeneously Ni-assisted cross-coupling reaction of aryl/vinyl iodides and thiocarboxylates. A range of sulphur-containing aryl as well as vinyl derivatives (15 examples) was achieved in high yields (up to 82%), mild reaction conditions and wide functional group tolerance.