A variety of poly(arylmethylgermanes) have been synthesized from aryldimethylgermanes in high yield via mild catalytic demethanative coupling using tetrakis(trimethylphosphine)dimethylruthenium as a convenient catalyst precursor. Polymerizations of germanes Me2GeArH (Ar = phenyl, p-tolyl, p-fluoro, p-trifluorotolyl, p-anisyl, and m-xylyl) proceed in neat monomer at room temperature. Catalyst removal can be effected by treatment of the reaction mixture with air, which gives polymer yields between 70% and 100%. Alternatively, separation of the catalyst by precipitation of the polymers from THF solution with methanol gives lower yields, but of somewhat higher molecular weight material. The new polygennanes are characterized by H-1 NMR and by gel permeation chromatography (GPC) using both polystyrene standards and light scattering methods. Molecular weights calculated by polystyrene analysis fall in the ranges of M-w = 3 x 10(3) to 7 x 10(3) and M-n = 2 x 10(3) to 6 x 10(3). Values obtained from Light scattering are approximately 60% and 82% higher, respectively, resulting in M-w measured by SEC/LS in the range 5 x 10(3) to 1 x 10(4), with M-w/M-n similar to 1.3. The absorption spectra of the polygermanes exhibit lambda(max) in the range 326-338 nm. Comparison of the properties of poly(phenylmethylgermane) prepared by catalytic demethanative coupling and Wurtz coupling of MePhGeCl2 with sodium revealed no significant differences.