Small amounts of polyvinyl alcohol (PVA; 0.5-1.5 wt.%) added to extraction resin was synthesized by suspension polymerization. Their effects on the separation of rare earths (RE) were then investigated by conducting a relative comparison with the performance of pure extraction resin. The supporter and extractant of extraction resin were styrene-divinyl benzene copolymer and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HEH[EHP]), respectively. The size of PVA added extraction resin was reduced by 40% particle size of pure extraction resin. Furthermore, a higher level of PVA addition, shorter effluent range and smaller resolution values were shown in the extraction. In constant PVA added extraction resin, more diluted effluent concentration, longer effluent range and bigger resolution values were shown in the extraction. This could be the result of the bonding force between the rare earths and the extraction resin due to the nature of the interaction between the OH(-) group in PVA and the OH(-) group in extractants such as HEH[EHP]. Thus, the bonding force between the RE and extractants was determined by the level of PVA in the resins and the acidity of the effluent solution became another important factor in the extraction performance of the rare earths. As a result, the optimal level of PVA addition and the concentration of effluent for RE (Gd and Tb) separation were determined to be 0.5 wt.% of PVA and 0.05 M HCl of effluent, respectively.