The pH plays a significant role on the formation of metalcomplex and subsequent extraction, and is proved to be one of main factors for DLLME. In order to attain high extraction effi-ciency, the effect of pH on the DLLME of complex Fe(II)-5-BrPADAP was investigated in the pH range of 3.0–8.0 with different acetic acid–sodium acetate buffer solution and sodium hydroxide for much higher pH.