Graphene's success has shown not only that it is possible to create stable, single-atom-thick sheets from a crystalline solid but that these materials have fundamentally different properties than the parent material. We have synthesized for the first time, millimeter-scale crystals of a hydrogen-terminated germanium multilayered graphane analogue (germanane, GeH) from the topochemical deintercalation of CaGe2. This layered van der Waals solid is analogous to multilayered graphane (CH). The surface layer of GeH only slowly oxidizes in air over the span of 5 months, while the underlying layers are resilient to oxidation based on X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy measurements. The GeH is thermally stable up to 75 °C; however, above this temperature amorphization and dehydrogenation begin to occur. These sheets can be mechanically exfoliated as single and few layers onto SiO2/Si surfaces. This material represents a new class of covalently terminated graphane analogues and has great potential for a wide range of optoelectronic and sensing applications, especially since theory predicts a direct band gap of 1.53 eV and an electron mobility ca. five times higher than that of bulk Ge.