In this paper, the advantages and disadvantages of germanium precipitation by PFS and tannic acid were compared, and the process idea of "distribution method" for efficient recovery of germanium from germanium hydrolysis residue was established. By adjusting different pH values, the step-by-step sedimentation method can make the iron ions in PFS hydrolyze sufficiently, and then effectively adsorb germanium in liquid phase and form coprecipitation. After solid-liquid separation of the precipitate, germanium concentrate can be obtained. The results show that the recovery of germanium is about 99.5% and the grade of germanium concentrate is over 7%. Through the test verification, the optimal economic and technical indexes can be achieved by adjusting the pH value to be about 9.5 and 7.5 respectively, adding polyferric sulfate in two steps, the weight ratio of adding amount to germanium in solution is 12:1, and aging in two steps for 6 hours respectively; the germanium residue can be returned to supplement the waste gas leaching system, so as to realize the closed cycle of the whole system.