Extraction of Am and Eu using mixtures of diphosphine dioxides (DPDO, e.g., (R₁)₂P(O)(CH₂)_nP(O (R₂)₂ where R₁, R₂ = Ph, Bu; n = 1,2), with and without chlorinated cobalt dicarbollide (CCD) in the polar diluents 1,2-dichloroethane (DCE), meta-nitrobenzotrifluoride (F-3 , bis-tetrafluoropropyl ether of diethylene glycol (F-8) and phenyltrifluoromethyl sulfone (FS-13) from HNO₃, HClO₄, LiNO₃ and LiClO₄ solutions has been investigated. The anomalous aryl strengthening (AAS) effect, i.e. the anomalous increase of extraction ability of methylene bridged diphosphine dioxides due to substitution of aromatic (i.e., phenyl) for alkyl (e.g., butyl or octyl) moieties (D_Am increases by three to four orders of magnitude), is only observed during the extraction of Am and Eu from acidic media. In salt media the AAS effect is weakly observed, and is practically absent in such diluents as F-3 and FS-13. The extraction isotherm in the case of DPDO with an observed AAS effect indicates the distribution coefficients of Eu decrease by a factor of two to three, even at the concentration ratio of DPDO:Eu = 50:1; however, these values decrease only by 10% for the DPDO that do not indicate an observed AAS effect. It is proposed that the presence of water in the diluent is necessary for manifestation of the AAS effect. The synergistic effects of adding chlorinated cobalt dicarbollide (CCD) with the DPDO that has been reported for other systems was also found to prevail in several of the systems investigated in this study. On addition of CCD with the DPDO, a considerable synergistic effect is observed (D_Am increases by three to four orders of magnitude) during Am and Eu extraction from nitrate media. In perchlorate media the synergistic effect is absent. The most probable reason for synergism in the presence of CCD is the higher hydrophobicity of the CCD anion as compared to the nitrate anion. The results of this work will be of utility in understanding existing and developing new extraction systems designed for the simultaneous removal of multiple radionuclides from acidic streams.