Liquid ion exchange is widely used for recovery of metals from aqueous solutions. The high molecular weight amines α-NA,4-ABA and imidazole derivative 4-CMePADPI as well as Cryptand C222 were used to recover Zn(II)from aqueous solutions as chloro complex anion ZnCl4=. Experiments were performed as a function of different variables such as concentration of hydrochloric acid for preparation of chloro complex anion ZnCl4= as well as concentration of hydrochloric acid for preparation of liquid anion exchange [HL]+Cl- in organic phase in addition of shaking time, from the other hand studied the organic solvent effect and stoichiometry for ion pair complex formation. Thermodynamic study shows anion exchange reaction for ZnCl4= to form ion pair complex was exothermic with α-NA and C222 but endothermic with 4-ABA and 4-CMePADPI.