We have employed synchrotron radiation photoemission spectroscopy to study the reaction mechanism, surface bonding, and thermal stability of 1-octadecanethiolate (ODT) self-assembled monolayers (SAMs) at Cl- and Br-terminated Ge(100) surfaces. Density functional theory (DFT) calculations were also carried out for the same reactions. From DFT calculations, we have found that adsorption of I-octadecanethiol on the halide-terminated surface via hydrohalogenic acid elimination is kinetically favorable on both Cl- and Br-terminated Ge surfaces at room temperature, but the reactions are more thermodynamically favorable at Cl-terminated Ge surfaces. After ODT SAM formation at room temperature, photoemission spectroscopy experiments show that Ge(100) and (111) surfaces contain monothiolates and possibly dithiolates together with unbound thiol and atomic sulfur. Small coverages of residual halide are also observed, consistent with predictions by DFT. Annealing studies in ultrahigh vacuum show that the Ge thiolates are thermally stable up to 150 degrees C. The majority of the surface thiolates are converted to sulfide and carbide upon annealing to 350 degrees C. By 430 degrees C, no sulfur remains on the surface, whereas Ge carbide is stable to above 470 degrees C.