Eight adducts of Rh-2(O2CCH3)(4) with axial pyridine derivatives that contain hydrogen-bonding amino and/or steric methyl substituents in the 2- and 6-positions have been prepared and examined by electronic absorption and LH NMR spectroscopy in solution and by elemental, IR, thermogravimetric, and X-ray diffraction analyses in the solid state. The results indicated that strong hydrogen bonding interactions between Rh-2(O2CCH3)(4) and axially coordinated pyridine derivatives with a 2- or 6-amino group occur in both solution and the solid state and contribute to the higher thermal stability of the molecular assembly of dirhodium complexes. It was demonstrated that such a combination of coordinate and hydrogen bonds is useful as a building tool in designing and constructing new organic-inorganic hybridized compounds and supramolecular architectures.