It was shown that a strong synergistic effect (S approximate to 4000) takes place when extracting manganese (II) from sulfate solutions with mixtures of bis(2,4,4-trimethylpentyl)dithiophosphinic acid (CYANEX 301) and trioctyl phosphine oxide (TOPO. The synergistic effect is caused by the formation of the mixed complex Mn-HR-TOPO. Analysis of the manganese partition between organic and aqueous phase as well as of the IR and electron paramagnetic resonance spectra of the extracts showed that manganese forms a hexacoordinated complex with the dithiophosphinate ions and TOPO with an octahedral geometry. The composition of the complex can be presented as MnR2.2TOPO.Examples of the possible use of the CYANEX 301 and trialkyl phosphine oxide (TAPO, CYANEX 923) mixtures when processing manganese-containing liquors are given.