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The aim of this work was to understand the main structural features and ways of formation of Ge-O bonds in organogermanium compounds under the conditions of Ar_nGeHal_4-n (Hal = halide) hydrolysis. The structural types of these compounds were considered, providing 11 blocks (<b>A</b>–<b>K</b>). The molecular structures of the novel compounds [(<i>p</i>-FC₆H₄)₃Ge]₂O (<b>1</b>), [(<i>p</i>-F₃CC₆H₄)₃Ge]₂O (<b>2</b>), and <i>cyclo</i>-[(<i>p</i>-F₃CC₆H₄)₂GeO]₄ (<b>3</b>) were studied through XRD (X-ray diffraction) analysis. The molecular structure of [(<i>p</i>-F₃CC₆H₄)₃GeO]₄Ge (<b>4</b>), representing a novel structural type, was also investigated. The data presented in this study will be important in the design of materials with useful properties based on group 14 element derivatives with element–oxygen bonding.