The stereoselective route toward new molecular and macromolecular compounds containing arylene−germylene−vinylene units is described. The reagents for germylative coupling reaction were 1,4-bis(dimethylvinylgermyl)benzene (1) and vinyl-and divinylarenes with ruthenium complexes (2a, 2b) as catalysts. NMR characterization of all isolated products, results of MS and elemental analysis for molecular compounds (3−5), and GPC for oligomers (6−8) are presented. Absorption and luminescence properties of the synthesized compounds are discussed and compared with those of model chromophores.