Cation exchange behaviour of Zn(II) on Dowex 50 W × 8 (H+form) resin has been studied in mixed solvents and non-aqueous HBr system. 20–90% organic solvents like Acetone, Methanol, Tetrahydrofuran, 1,4-Dioxane, Ethanol in conjunction with 0.2M or 0.5M HBr were used as eluants. Separation of zinc from binary mixtures containing Ga(III), Th (IV), Ce(III), Fe(III), Ba(II), Co(II), Cu(II), Mn(II), Ni(II), Ca(II), Ti(IV), Li(II), Na(I), K(I) have been studied. Separation of zinc from multicomponent mixtures have been accomplished. The proposed method has been applied for the analysis of alloys, environmental and pharmaceutical samples.