The adsorption and decomposition of AlCl3 on Ge(100) was studied using scanning tunneling microscopy (STM) and high-resolution core-level photoemission spectroscopy (HRCLPES). Through the analysis of the STM image and Ge 3d and Cl 2p core-level spectra of AlCl3 on Ge(100), we found that an AlCl3 molecule reacts with two Ge atoms via a cycloaddition reaction, which forms Cl−Ge and AlCl2−Ge without breaking AlCl3. Additionally, by considering valence shell electron pair repulsion (VSEPR) arguments, the effect of molecular structure on the surface chemistry was explained. To our knowledge, the adsorption of Lewis acid molecules on a semiconductor surface has not been studied in detail. These are the first results for the adsorption structures of Lewis acid molecule on Ge(100).