A separation method of zirconium and hafnium according to an example of the present invention comprising, mixing step to prepare a crude liquid for extraction, by mixing a sulfuric acid solution including zirconium and hafnium, a catalyst, and an acidic extractant; and first extraction step to form a first extract solution layer comprising the acidic extractant in which the hafnium has been extracted and a sulfuric acid solution layer separated from the first extract solution layer, wherein the acidic extractant comprises any one selected from a group consisting of D2EHPA (Di-(2-ethylhexyl)phosphoric acid), PC88A (2-Ethylhexyl phosphonic acid mono-2-ethylhexyl ester), and a combination thereof. The separation method not only saves the amount of extractant used but also increases separation effect of zirconium and hafnium known to be difficult for separating each other, without using no toxic compound such as cyan.