The effect of chemical composition on the bonding environment of Cu, in a series of Ti1-x Cux and TiN/Cu films, is studied using X-Ray Absorption Spectroscopies (XAFS) at the Cu-K-edge. The EXAFS analysis reveals that in all studied samples Cu is amorphous. However, its bonding environment depends on the chemical composition. More specifically, in the Ti1-xCux films, Cu is coordinated with Ti and Cu and belongs both to intermetallic TiCu and to an amorphous Cu matrix. The coordination number of Cu, i.e., the sum of Ti and Cu first neighbours, increases systematically from 6.3 ± 0.7 to 10.6 ± 0.9 when the Cu content increases from 24.1 to 52.7 at%. On the contrary, in the TiN/Cu films, the type of atoms that consists the 1st nearest neighbour shell of Cu varies as a function of the Cu concentration. More specifically, in the TiN/Cu film with the lowest Cu content (27.3 at%), intermetallic TiCu is detected. At intermediate Cu concentration (37.8 at%), Cu is bonded to both Ti and Cu atoms. Finally, in the TiN/Cu film with the highest Cu content (67.7 at%), Cu is metallic.