The competitive sorption of Cu(II) and Eu(III) ions from aqueous solutions by olive-cake carbon, has been investigated by potentiometry at pH 6, I = 0.1 M NaClO 4 , 25°C and under normal atmospheric conditions. Evaluation of the experimental data supports the formation of inner-sphere surface complexes and results in the calculation of the formation constant of the surface complexes ((=S-O) 2 Cu), which is found to amount log β Cu = 5.3 ± 0.3. Addition of competing Eu(III) ions in the aqueous system leads to replacement of the Cu(II) by the competitor metal ion. Evaluation of the potentiometric data obtained from competition experiments indicates an ion-exchange mechanism. The formation constant of the Eu(III) species sorbed on olive cake carbon is found to be log β Eu = 5.1 ± 0.5. Comparison of the complex formation constants of the olive-cake carbon with the corresponding complex formation constants for of olive cake and humic acid with the two metal ions, indicates that the same type of active sites is responsible for the metal ion complexation on the surface of the different types natural organic matter (e.g. olive-cake carbon, olive-cake and humic acid).