Abstract: | The rediscovery of graphene in 2004 has started an enormous chase in the research of 2D materials. A new family of layered 2D materials consisting of the 14th group elements beyond carbon has already been reported. Here, a new methodology in germanene chemistry is presented using germanane (Ge6H6) as a stable and easily accessible starting material for effective synthesis of novel germanene derivatives. The modification procedure utilizing strong bases—alkali metal arenides—for deprotonation of germanane and its subsequent functionalization with p‐nitrobenzyl bromide is described. Functionalization of germanene is confirmed by FT‐IR, Raman, and XPS spectroscopy as well as by X‐ray diffraction analysis. |