The new ligand 4-PyCH2OCS2Na, that combines two different donor groups in one molecule (a soft -CS2- group and a hard pyridine moiety), has been synthesized. The ligand coordinates to a [(bipy)Re(CO)(3)](+) center in a monodentate fashion through one of its soft sulfur atoms, leaving the hard pyridine terminus free for further coordination chemistry. Using a Ni(II) dithiophosphonate linker, the heterometallic {[CH3OCH2CH2OP(An)S-2](2)Ni}[4-PyCH2OCS2Re(bipy)-(CO)(3)](2) Complex is obtained, through the coordination of two pyridine groups to the Ni(II) center. This simple, high-yield stepwise strategy toward heterometallic complexes could be easily transferable to other 1, 1-dithiolate ligands and used in combination with a large variety of luminescent metallic systems.