The invention relates to a chitosan/persimmon tannin composite material and a preparation method and application thereof in germanium recovery. The preparation method adopts the technical scheme with the following steps of putting chitosan into a three-mouth flask, adding a proper amount of ethyl alcohol solution, dripping an epichlorohydrin solution, reacting at certain temperature, cooling, sucking and filtering, and washing to be at neutral state, so as to obtain an intermediate product; putting the persimmon tannin into the other reaction container, adding deionized water, adjusting the pH (potential of hydrogen) value to 9 to 10, adding the intermediate product, stirring for 6h at the temperature of 40 to 50 DEG C, cooling, sucking and filtering, and washing to be at neutral state, so as to obtain the chitosan/persimmon tannin composite material CS-Cl-PT. The prepared chitosan/persimmon tannin composite material has the advantages that the germanium can be selectively absorbed from a mixing solution of germanium and arsenic, the resource is saved, the environment-friendly and clean effects are realized, and the application value is wide.