Synergistic effect of neutral bidentate ligands, L, such as 1,10-phenanthroline(phen), 2,9-dimethyl-1,10-phenanthroline(dmp), and 2,2′-bipyridine(bpy), and of neutral unidentate ligands TBP and TOPO have been studied in the extraction of Mn(II) labeled with54Mn, using 2-thenoyl-trifluoroacetone(HTTA) in various organic solvents. The following factors play an important role in the synergistic extraction involving bidentate ligands; two-phase partition of bidentate ligands, their protonation and complex formation with Mn(II) in the aqueous phase. The mixed ligand complex, Mn(TTA)2L, is formed in all bidentate ligand systems. The adduct formation constant (αS,1) decreases in the following order; phen (lg αS,1=12.64) > dmp(11.32)> · bpy(8.54) in the cyclohexane system. This order is ascribed to the bacisity and the steric effect of the bidentate ligands. Organic solvents influence both the adduct formation and the partition of the ligands, and αS,1 decreases in the order cyclohexane>carbon tetrachloride>chlorobenzen ∼= benzene>chloroform.