A thermochemical study of three germanium allotropes by differential scanning calorimetry (DSC) and oxidative high-temperature drop solution calorimetry with sodium molybdate as the solvent is described. Two allotropes, microcrystalline allo-Ge (m-allo-Ge) and 4H-Ge, have been prepared by topotactic deintercalation of Li₇Ge₁₂ with methanol (m-allo-Ge) and subsequent annealing at 250 °C (4H-Ge). Transition enthalpies determined by differential scanning calorimetry amount to 4.96(5) ± 0.59 kJ/mol (m-allo-Ge) and 1.46 ± 0.55 kJ/mol (4H-Ge). From high-temperature drop solution calorimetry, they are energetically less stable by 2.71 ± 2.79 kJ/mol (m-allo-Ge) and 5.76 ± 5.12 kJ/mol (4H-Ge) than α-Ge, which is the stable form of germanium under ambient conditions. These data are in agreement with DSC, as well as with the previous quantum chemical calculations. The morphology of the m-allo-Ge and 4H-Ge crystallites was investigated by a combination of scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. Even though the crystal structures of m-allo-Ge and 4H-Ge cannot be considered as truly layered, these phases retain the crystalline morphology of the layered precursor Li₇Ge₁₂. Investigation by diffuse reflectance infrared Fourier transform spectroscopy and UV–vis diffuse reflectance measurements reveal band gaps in agreement with quantum chemical calculations.