The present work envisages a chelation driven, facile, selective, and rapid method for uranium(VI) separation from a (U, Th) mixture using 1-hydroxy-2-pyridone (1,2-HOPO). Herein, U(VI) was selectively precipitated as the neutral [UO2(HOPO)2(H2O)]·nH2O (orange colored) complex while Th(IV) and other metal ions remained in the solution. The pH of the medium played a key role in facilitating the separation process.