A series of 10 poly(urethanes) were synthesized by solution polymerization from bis(chloroformates) and aromatic diamines, containing both silicon or germanium as central atom. So, the polymers prepared contain two silicon atoms or two germanium atoms exclusively or combinations of both. Me, Et, and Ph groups were bonded to the central atoms according to the nature of the monomers employed. Poly(urethanes) were characterized by FTIR, H-1, C-1, and Si-29 NMR spectroscopy and the results agreed with the proposed structures. Additionally, intrinsic viscosity values were established in DMSO solutions and thermal analyses were developed. In all cases, thermostable oligomers were obtained, which showed a degradation process beginning at similar to 240-260 degrees C. Polymers showed a thermal dependence with the nature of the heteroatom employed. Thus, in general, when germanium was used as central atom, the thermal stability was higher than the polymers containing silicon which agrees with the lower polarity and higher energy of the C-Ge bond in comparison with the C-Si one. (C) 2008 Wiley Periodicals, Inc.