The extraction of Eu(III) by dinonylnaphthalenesulfonic acid (HDNNS) in benzene from nitrate and perchlorate solutions has been investigated. For nitrate solutions the ionic strength of the aqueous phase was kept constant at 0.1M using NaNO3–HNO3 mixtures. The Eu distribution was measured at different temperatures. The following stoichiometric formulae for the Eu species in benzene were derived: Eu(NO3) (Hn–1 (DNNS)n)2 and Eu(Hn–1 (DNNS)n)3, from the nitrate and perchlorate medium respectively (n being a small number, e.g. 1, 2 or 3). The equilibrium constants were calculated and the thermodynamic parameters of the system were determined. When adding dibenzo-24-crown-8, dicyclohexyl-18-crown-6 or trioctylphosphine oxide, no synergism, but rather antagonism was observed.