Graphical abstractThe structure around the absorbing atom in the dicomplexes of 6,6'-bis (5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzo[1,2,4]triazin-3-yl) [2,2]bipyridine, CyMe4-BTBP, with americium(III) and europium(III) have been determined by means of Am and Eu L3 edge EXAFS spectroscopy in a series of solvents used to separate these metal ions using solvent extraction. The obtained structural information has been correlated with previously reported solubility and selectivity data as well as ionic radii in general terms.-3 -Abstract Separation of trivalent actinoid (An(III)) and lanthanoid (Ln(III)) ions is extremely challenging due to their similar ionic radii and chemical properties. Poly-aromatic nitrogen compounds acting as tetradentate chelating ligands to the metal ions in the extraction, have the ability to sufficiently separate An(III) from Ln(III). One of these compounds, 6,6'-bis (5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzol[1,2,4]