This paper reports a novel solid-phase extraction scheme for the group separation of high field strength elements (HFSE) Nb, Ta, Zr, and Hf from Ti-, Fe-, and Al-rich geological materials. The solid-phase extraction resin was prepared by impregnating hydrophobic microporous polymer beads with N-benzoyl-N-phenyl-hydroxylamine (BPHA) dissolved in chloroform followed by evaporating the solvent. Geological samples were attacked with concentrated hydrofluoric acid and treated with perchloric acid fuming to remove silica. The rock sample was then made up with 4 M HCl solution and loaded onto an extraction column packed with the solid-phase extraction resin. All the major rock constituents (Ca, Mg, K, Na, Al, Fe, Mn, and Ti) were eluted with 4 M hydrochloric acid followed by 2 M sulfuric acid containing 1% v/v H2O2 The HFSE were retained on the extraction column and subsequently eluted with 0.5 M oxalic-02 M hydrofluoric acid or 5 M hydrofluoric acid. The potentialities of the;separation scheme are highlighted by the easy separation of HFSE from the rock matrix and Ti. The solid-phase extraction is superior to liquid-liquid extraction in analytical separations with respect to selectivity and manipulation.