Extraction of Am(III) and Ln(III) from NaClO4 medium with di(2-ethylhexyl)dithiophosphoric acid (DEHDTP), di(2-ethylhexyl)monothiophosphoric acid (DEHMTP), di(2-ethylhexyl)monothiophosphinic acid (DEHMTPI), dihexyldithiophosphinic acid (DHXDTPI), diheptyldithiophosphinic acid (DHPDTPI), dioctyldithiophosphinic acids (DODTPI), dinonyldithiophosphinic acid (DNDTPI), di(1-methylheptyl)dithiophosphinic acid (DMHDTPI) and di(2-ethylhexyl)dithiophosphinic acid (DEHDTPI) in xylene has been investigated. The order of the extraction selectivity for Am(III) is DEHDTPI > DEHDTP > DEHMTPI > DEHMTP, DHPDTPI > DODTPI > DHXDTPI > DNDTPI, DMHDTPI > DEHDTPI > DODTPI, for extractants with 2-ethylhexyl alkyl, straight chain alkyl, branch chain alkyl, respectively. Using 0.1 mol/l NaClO4 solution as aqueous phase, the slope values of the logD-pH and logD-logC curves are not integers, and the slope values for Am(III) are slightly higher than those for Eu(III), for all extractants. The relationship between the slope value and extraction conditions can be described as: logS = alg(CHA/CMS/4)+b. In the presence of macro Eu(ClO4)3, the formula, logSFAm/Ln = B-2log(CHL-DLn/(DLn + 1)CEu), can well describe the relationship between separation factor and the extraction condition. A high separation factor (SFAm/Eu = 2500) is obtained by solvent extraction with 0.5 mol/1 DEHDTPI in toluene from 1 mol/l NaNO3 solution.