Hybrid organic/inorganic interfaces could pave the way to chemically designed or new multifunctional electronic devices, in particular in the spintronics field where, for instance, the interfacial spin polarization can be tuned through chemical interactions and surface modifications. We report herein, for the very first time, the assays of self-assembled monolayers (SAMs) formation on Mn5Ge3 surface. Interestingly, Mn5Ge3 is a ferromagnetic metal possessing interesting features for spintronics such as a high Curie temperature, a capability to grow epitaxially on Ge germanium that is a key point for integration in the mainstream Si technology. Mn5Ge3 thin films are synthesized by molecular beam epitaxy under ultra-vacuum condition. We studied the Mn5Ge3 surface prior to deposition of SAMs, meaning the surface exposed to air and different solvents, by XPS and contact angle measurements leading to the value of the surface tension of this surface. Then SAMs of octanethiol and perfluorodecanethiol are formed on Mn5Ge3 surface at room temperature. The best experimental conditions to form the SAMs are found for an immersion time of 36 h and a concentration of 4 mM. (C) 2018 Elsevier B.V. All rights reserved.