The dependence of electronic structure and electrical properties on molecular and supermolecular structure in the case of plasma deposited carbon-germanium glasses is reported. Particular attention is devoted to thin films produced from tetramethylgermane in the three-electrode reactor. An attempt is done to correlate the differences in electronic structure with changes of molecular structure. To this end, investigations of chemical constitution. mass density, infrared absorption and Raman spectroscopy are realized. The obtained results allow to state that the transition from amorphous insulator to amorphous semiconductor proceeds due to appearance of specific nanonstructure consisting in separation of germanium reach clusters from carbon matrix. Based on XPS spectroscopy and scanning probe microscopy (SPM) it is proved that germanium clusters are not randomly distributed in the carbon matrix but agglomerate forming domains with size of 60-100 nm. An average distance between grains inside the domain is respectively shorter than that separating two domains.