In the last decade, research on 2D materials has expanded massively due to the popularity of graphene. Although the chemical engineering of two-dimensional elemental materials as well as heterostructures has been extensively pursued, the fundamental understanding of the synthesis of 2D materials is not yet complete. Structural parameters, such as buckling or the interface structure of a 2D material to the substrate directly affect its electronic characteristics. In order to proceed the understanding of the element-specific growth and the associated ability of tuning material properties of two-dimensional materials, we performed a study on the structural evolution of the promising 2D material germanene on Ag(111). This study provides a survey of germanium formations at different layer thicknesses right up to the arising of quasi-freestanding germanene. Using powerful surface analysis tools like low-energy electron diffraction, x-ray photoelectron spectroscopy, and x-ray photoelectron diffraction with synchrotron radiation, we will reveal the internal and interfacial structure of all discovered germanium phases. Moreover, we will present models of the atomic and chemical structure of a $$\hbox {Ag}_2\hbox {Ge}$$ Ag 2 Ge surface alloy and the quasi-freestanding germanene with special focus on the structural parameters and electronic interaction at the interface.