The extraction of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from HNO3solutions by phosphoryl-containing podands of various structures has been studied. It has been found that the maximum extraction of rare earth elements is exhibited by reagents containing one ether oxygen atom in the molecule, bound to diphenylphosphoryl or ditolylphosphoryl containing podands towards REE varies in a wide range, depending on the number of oxygen atoms in the polyether chain and the structure of the fragment connecting the ether oxygen atom with the terminal PO group. The podand structure which ensures a polydentate coordination of the reagent molecule to yield chelate complexes is favourable for REE extraction. The replacement of phenyl radicals in the podand VII molecule for butyl ones (compound IX) drastically reduces REE extraction. REE extraction by podands VII and VII increase from La to Lu with a decrease in the radii of extracted ions