The extraction of Er(III) and Lu(III) from thiocyanate media with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (EHEHPA) and also with mixtures of EHEHPA and thenoltrifluoroacetone (HTTA) or tri-n-octylphosphine oxide (TOPO) or bis 2-ethylhexyl sulfoxide (B2EHSO) in benzene has been studied systematically. Synergistic effects have been observed with mixtures of EHEHPA+HTTA or TOPO. On the other hand, antagonistic effects have been observed with mixtures of EHEHPA+B2EHSO. These extraction data have been analyzed theoretically with the aid of a computer by taking into account complexation of the metal in the aqueous phase by SCN– and plausible complexation in the organic phase. The extraction constants of the various product species have been deduced by non-linear regression analysis. The stability constants for the thiocyanate complexes of the metal ions have also been determined.