AbstractElectronic, optoelectronic, and other functionalities of semiconductors are controlled by the nature and density of carriers, and the location of the Fermi energy. Developing strategies to tune these parameters holds the key to precise control over semiconductors properties. We propose that ligand exchange on superatoms can offer a systematic strategy to vary these properties. We demonstrate this by considering a WSe₂ surface doped with ligated metal chalcogenide Co₆Se₈(PEt₃)₆ clusters. These superatoms are characterized by valence quantum states that can readily donate multiple electrons. We find that the WSe₂ support binds more strongly to the Co₆Se₈ cluster than the PEt₃ ligand, so ligand exchange between the phosphine ligand and the WSe₂ support is energetically favorable. The metal chalcogenide superatoms serves as a donor that may transform the WSe₂ p-type film into an n-type semiconductor. The theoretical findings complement recent experiments where WSe₂ films with supported Co₆Se₈(PEt₃)₆ are indeed found to undergo a change in behavior from p- to n-type. We further show that by replacing the PEt₃ ligands by CO ligands, one can control the electronic character of the surface and deposited species.