In order to remove fluorine from a zinc containing solution before zinc electro-refining in lower cost, fluorine is removed by adsorption from a zinc containing solution (leached solution) utilizing the character of the predetermined iron compound or zinc compound which can adsorb fluorine in an acid solution and desorb fluorine in an alkaline solution. The fluorine adsorbent/desorbent having adsorbed fluorine is treated in an alkaline solution, to desorb the fluorine. This makes it possible to regenerate the fluorine adsorbent/desorbent. Further, an electrolytic solution for zinc electro-refining can be prepared in lower cost, thus total zinc refining costs can be reduced.