Abstract. X-ray Absorption Spectroscopy (XAS) has been used to probe the local structure of copper(I) complexes containing scorpionate ligands. The EXAFS analysis, performed by using the GNXAS package, has permitted the identification of the local environment of the copper site. Copper is found to be 4-fold coordinated with two sets of Cu-N and Cu-P interactions describing a quasi planar figure, in the case of {Cu[(C₆H₅)₂PCH₂CH₂P(C₆H₅)₂][H₂B(tz^NO2)₂]}. An additional coordination is revealed for the copper complex of bis(1,2,4-triazol-1-yl)acetate due to the interaction of the copper with the acetate of the scorpionate ligand. XANES spectra behaviour confirms the occurrence of copper in the +1 oxidation state.