The recent discoveries of silicene, germanene, and stanene, commonly denoted as Xenes (with X being Si, Ge, Sn), and their ligand-functionalized" Xane" derivatives, brings to the forefront an important class of two-dimensional (2D) elementary crystals. Similar to graphene, these materials are comprised of group IV atoms arranged in a honeycomb lattice, but with varying degrees of buckling that inherently stem from the interplay of sp 2 and sp 3 hybrid bonds. So far, Xenes were synthesized as epitaxially grown monolayers on substrates. An overview of the state-of-the-art on the Xenes-on-substrates will be here given. The silicene-on-silver will be taken as a representative example of the Xenes. Generally, two aspects qualify the epitaxy of Xenes on substrates, the emergence of a vertically buckled lattice and the strong interaction with the hosting substrate. The former fact may offer a potential to access to (and …