The synergic extraction of the different lanthani-des, except Pm and Lu, by thenoyltrifluoroacetone (HTTA) and triphenylphosphine oxide (TPPO) mixture in benzene from an aqueous perchlorate medium of constant ionic strength of 0·2 was investigated. It was found that the main adduct extracted contains the lanthanide chelates together with two TPPO molecules. The different extraction and formation constants for the lanthanides investigated have been determined. The variations of the logarithmic values of the chelate extraction constant and the adduct formation constant with the different lanthanides was discussed in the light of the tetrad and the inclined-W effects. The experimental results showed that the nature of coordination by adduct formation for the Yb-Sm group is different than that of the Pr-La group.