Continued scaling of electronic devices shows the need to incorporate high mobility alternatives to silicon, the cornerstone of the semiconductor industry, into modern field effect transistor (FET) devices. Germanium is well-poised to serve as the channel material in FET devices as it boasts an electron and hole mobility more than twice and four times that of Si, respectively. However, its unstable native oxide makes its passivation a crucial step toward its potential integration into future FETs. The International Roadmap for Devices and Systems (IRDS) predicts continued aggressive scaling not only of the device size but also of the pitch in nanowire arrays. The development of a vapor-phase chemical passivation technique will be required to prevent the collapse of these structures that can occur because of the surface tension and capillary forces that are experienced when tight-pitched nanowire arrays are processed via liquid-phase chemistry. Reported here is a vapor-phase process using hexanethiol for the passivation of planar Ge(100) substrates. Results benchmarking it against its well-established liquid-phase equivalent are also presented. X-ray photoelectron spectroscopy was used to monitor the effectiveness of the developed vapor-phase protocol, where the presence of oxide was monitored at 0, 24, and 168 h. Water contact angle measurements compliment these results by demonstrating an increase in hydrophobicity of the passivated substrates. Atomic force microscopy monitored the surface topology before and after processing to ensure the process does not cause roughening of the surface, which is critical to demonstrate suitability for nanostructures. It is shown that the 200 min vapor-phase passivation procedure generates stable, passivated surfaces with less roughness than the liquid-phase counterpart.