The adsorption structures and thermal desorption behavior of C 2 H 2 on Ge͑100͒ were studied in ultrahigh vacuum by scanning tunneling microscopy ͑STM͒ and temperature programmed desorption ͑TPD͒. The STM investigation revealed that, at low coverage, C 2 H 2 initially adsorbs onto the Ge͑100͒ surface with two types of configurations: ͑i͒ a diconfiguration on top of a single Ge-Ge dimer ͑on-top͒ and ͑ii͒ a tetra-configuration parallel to the dimer axes, bridging two neighboring Ge dimers (p-bridge͒. TPD measurements show that chemisorbed C 2 H 2 desorbs from Ge͑100͒ nondissociatively with two different desorption features, denoted as ␣ ͑520 K͒ and  ͑560 K͒. In addition, it was found that the desorption of C 2 H 2 follows first order kinetics for both states and that the desorption energies of the ␣ ͑520 K͒ and  ͑560 K͒ states are 1.3 and 1.4 eV, respectively. STM studies of the adsorption of C 2 H 2 at various Ge surface temperatures indicate that the ␣ and  features correspond to the on-top and p-bridge configurations, respectively.