In view of the waste of W-Re alloy, the electrochemical dissolution method was used to make W, Mo and Rre completely dissolved in the alkaline solution of sodium hydroxide, and then the selective precipitation separation of the electrolytic solution were performed.by using calcium chloride to precipitate W-Mo and potassium chloride to precipitate Re. The results show that: (1)The suitable process parameters for electrochemical dissolution of W-Re alloy waste are: cell voltage 2.5V, NaOH concentration 100g/L, electrolysis temperature 30-40℃, electrode distance 20-30mm, and the total W-Re ion concentration is controlled at 30-35g/L. Under these conditions, the dissolution rate of W, Mo and Re are all more than 99%, the current efficiency is over 99%, and the wire waste is better than the block waste to be eletrochemically dissolved. (2)The optimum technological parameters for the selective chemical precipitation separation of W-Re electrolytic solution are: reaction temperature 80℃, CaCl₂ dosage 3 times of theoretical dosage, OH^_- concentration 9.5g/L, W ion concentration 23.18g/L, reaction time 2h. Under these conditions, the precipitation rates of W and Mo are 99.86% and 99.55%, respectively. (3)After the above two processes, the recovery rates of W and Mo are 98.86% and 98.55%, respectively. The morphology of CaWO₄/CaMoO₄ mixture is spherical, and KReO₄ white crystals are obtained.