The cyclic alkyl(amino) carbene (cAAC:)-stabilized acyclic germylones (Me₂-cAAC:)₂Ge (1) and (Cy₂-cAAC:)₂Ge (2) were prepared utilizing a one-pot synthesis of GeCl₂(dioxane), cAAC:, and KC₈ in a 1:2:2.1 molar ratio. Dark green crystals of compounds 1 and 2 were produced in 75 and 70% yields, respectively. The reported methods for the preparation of the corresponding silicon compounds turned out to be not applicable in the case of germanium. The single-crystal X-ray structures of 1 and 2 feature the C–Ge–C bent backbone, which possesses a three-center two-electron π-bond system. Compounds 1 and 2 are the first acyclic germylones containing each one germanium atom and two cAAC: molecules. EPR measurements on compounds 1 and 2 confirmed the singlet spin ground state. DFT calculations on 1/2 revealed that the singlet ground state is more stable by ∼16 to 18 kcal mol^–1 than that of the triplet state. First and second proton affinity values were theoretically calculated to be of 265.8 (1)/267.1 (2) and 180.4 (1)/183.8 (2) kcal mol^–1, respectively. Further calculations, which were performed at different levels suggest a singlet diradicaloid character of 1 and 2. The TD-DFT calculations exhibit an absorption band at ∼655 nm in n-hexane solution that originates from the diradicaloid character of germylones 1 and 2.