A method of recovering antimony and bismuth from copper electrolyte comprises the steps of immersing a pure copper material in the copper electrolyte, so that the iron ions are reduced from Fe.sup.3+ ions to Fe.sup.2+ ions, using a mixture of dilute sulfuric acid and sodium chloride adjusting the acidity or acidic concentration, to selectively elute the bismuth and antimony wherein if the final concentration of bismuth is adjusted to be 0.02 g/l or less in the bismuth election, it is possible to keep the maximum concentration of bismuth in the antimony eluate in the elution of antimony after selective bismuth elution to 0.01 g/l or less.