The influence of chemical structure of ester alkyl group of mono-alkyl isopropylphosphonates on the extraction behaviours of rare earth has been studied. The mono-alkyl isopropylphosphonate bearing β-substituted ester alkyl group shows high K_(ex) value, which is evidently depressed, usually in two orders of magnitude, by introducing a branch chain on the α-position of the ester alkyl group. The steric effect of ligand is usually enhanced due to the characteristic lanthanide contraction.z2The extraction chemistry of rare earths by mono-amylnonyl isopropylphosphonates (MANPP) was studied in detail The thermodynamic function was estimated and the “tetrad effect” between K_(ex) value or △G value and atomic number was observed. In addition, the composition and structure of the coordinated compound was studied. As demonstrated by the experimental data, the extractive separation of Sm and Nd by MANPP in chloride solution was better than that in nitrate system. The influence of chemical structure of ester alkyl group of mono-alkyl isopropylphosphonates on the extraction behaviors of rare earth has been studied. The mono-alkyl isopropylphosphonate bearing β-substituted ester alkyl group shows high K_ (ex) value, which is evidently depressed, usually in two orders of magnitude, by introducing a branch chain on the α-position of the ester alkyl group. The steric effect of ligand is usually enhanced due to the characteristic lanthanide contraction. z2 The extraction chemistry of rare earths by mono-amylnonyl isopropylphosphonates MANPP) was studied in detail The thermodynamic function was estimated and the “tetrad effect” between K_ (ex) value or ΔG value and atomic number was observed. In addition, the composition and structure of the coordinated compound was studied. As demonstrated by the experimental data, the extractive separation of Sm and Nd by MANPP in chloride solution was better than that in nitrate system.