A series of tris[(2-methoxymethyl)phenyl]germanes with a substituent on germanium was prepared and their solid-state and solution structures were investigated by means of X-ray crystallography and NMR spectroscopy to elucidate the effect of the substituent on the hypercoordination of the germanium atom in triarylgermanes. It was shown that when the substituent is a halogen, the triarylgermanes tend to be pentacoordinated trigonal bipyramidal while the triarylgermane is tetrahedral with no coordination when the substituent is a phenyl group. The methyl derivative is a monocapped tetrahedron.