The invention discloses a method for recycling elemental antimony in pentavalent antimony wastewater through photoelectric coupling. The method is characterized by comprising the following steps: reducing pentavalent antimony in water into trivalent antimony by using hydrated electrons; reducing trivalent antimony in the water into antimony by using an electrochemical reduction method so as to recycle antimony in the water. According to the method, a reduction material capable of generating hydrated electrons under excitation of light irradiation can be used as a source of the hydrated electrons; the secondary pollution is low; the hydrated electrons generated after excitation of light irradiation are capable of efficiently reducing pentavalent antimony which is relatively difficultly removed in the water into trivalent antimony which is relatively easily removed; the method is further combined with the electrochemical reduction method for reducing trivalent antimony in the water intoantimony, so that pentavalent antimony which is difficultly directly electrically deposited and recycled can be converted into elemental antimony; the antimony can be recycled; the method is stable and reliable, and is high in repeatability.