Two new divalent metal(II) aminodiphosphonates with layered structure, namely, Cu(H3L1)2·2H2O (1), [H4L1=methyl-N(CH2PO3H2)2] and Cd2(H2L2)4(2), [H4L2=n-propyl-N(CH2PO3H2)2] were synthesized and characterized. The Cu(II) ions in complex 1 are octahedrally coordinated by four oxygen atoms from two chelating ligands and two phosphonate oxygen atoms from two neighboring Cu(H3L1)2 units. The Cu(H3L1)2 units are interconnected by bridging phosphonate groups, forming a 2-D metal phosphonate layer. The structure of complex 2 contains two unique Cd(II) ions octahedrally-coordinated by six phosphonate oxygen atoms from four H2L2 diphosphonate anions. Corrosion inhibition performances of 1 and 2 were also compared with each other in order to study the effect of combinations of externally added Cd/H4L2 and Cu/H4L1 (1:1 ratio) on corrosion rates of carbon steel. It was found that at pH 3.0, Cd/H4L2 or Cu/H4L1 combinations do not have noticeable corrosion inhibition efficiency for carbon steel. In contrast, at pH 7.0, higher corrosion inhibition efficiency was achieved for Cd/H4L2. Physical characterizations such as scanning electron microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR) were applied to study the corrosion specimens and film material.