The invention discloses a method for separating antimony and iron in antimony and iron mixed solution through extraction-vulcanization phase inversion, and belongs to the field of nonferrous metallurgy. The method comprises the steps that iron powder is firstly used for reducing high valence antimony and iron ions into ferrous ions and antimony trivalent ions in the low valence, filtering and separating are carried out, a low-valence antimony and iron solution is obtained, a quaternary ammonium salt extraction agent is used for extracting and separating antimony from the solution, an antimony-rich organic phase and ferrous extraction raffinate are obtained, and the ferrous extraction raffinate can be directly subject to opening; the antimony-rich organic phase is not subject to reverse extraction, and directly subject to vulcanization phase inversion, antimony sulfide is generated, and through conversion, the organic phase is subject to ammonia washing to regenerate the quaternary ammonium salt extraction agent. Through the method, through valence state adjusting and selective extraction procedures, the separation problem of antimony and iron can be solved, the antimony and iron can be thoroughly separated, the creative vulcanization phase inversion is used for directly finishing precipitation separation of antimony, the antimony sulfide product can be obtained through one step, the flow is simplified, the reagent consumption is reduced, and the problem of antimony and iron separation and separated use in the wet method antimony smelting process can be solved.