Acylgermanes have been subject of great interest recently because of their low toxicity and the applicability as sources for germanium-centered radicals for visible-light induced free radical polymerization processes. We report on a novel and versatile method for the synthesis of tetraacylgermanes allowing the preparation of various tetra-substituted acylgermanes 1a–m. The formation of these derivatives was confirmed by NMR spectroscopy, mass spectrometry, and X-ray crystallography. UV–vis absorption spectra of the prepared compounds reveal absorption in the visible region. This transition was assigned by TD-DFT calculations. It enabled a general screening of the influence of different substitution patterns on the absorption properties. The radical formation upon irradiation was confirmed by TR-EPR spectroscopy.