In this work, a structural analysis of Ge layers deposited by molecular beam epitaxy (MBE) on Ag(1 1 1) surfaces with and without an AlN buffer layer have been investigated by x-ray Absorption Spectroscopy (XAS) at the Ge-K edge. For the Ge layers deposited on h-AlN buffer layer on Ag(1 1 1) an interatomic Ge–Ge distance RGe−Ge = 2.38 Å is found, typical of 2-Dimensional Ge layers and in agreement with the theoretical predictions for free standing low-buckled Germanene presented in literature. First principles calculations, performed in the density functional theory (DFT) framework, supported the experimental RHEED and XAS findings, providing evidence for the epitaxial 2-D Ge layer formation on h-AlN/Ag(1 1 1) template.