The synthesis and structural characterization of the vitamin B12 derivatives 9 and 10 equipped with a peripheral EDTA (ethylenediaminetetraacetic acid) binding site is described. It is based on the condensation of an activated ester of cobester- c-acid with ethane-1,2-diamine or 2-aminoethanol followed by acylation of the resulting amines with the monoanhydride 8 of EDTA. The title compounds 9 and 10 can be used as modifiers for metal oxide semiconductor electrodes and are potential precursors for the synthesis of bimetallic, supramolecular catalysts.