AbstractIn this study, 7‐(4‐ethyl‐1‐methyloctyl)‐8‐quinolinol (HL, Kelex 100) and 5,8‐diethyl‐7‐hydroxydodecane‐6‐oxime (LIX 63, HA) were employed to recover Ge(IV) from sulfuric acid solutions in the presence of singly charged inorganic anions. Under comparable conditions, the germanium extraction efficiency was in the order Cl−<NO3−<I−<<CNS−. In the presence of thiocyanate ion, the germanium complexes extracted by Kelex 100 and LIX 63 were [GeL3]+[CNS]− and Ge(OH)2A(CNS) respectively. An increase in the pH values was shown to lead to a decrease in the extraction of Ge(IV) with HL from sulfate‐thiocyanate solutions. At pH values of ≥5.9, the degree of germanium recovery is <2.0 % which makes stripping with alkaline aqueous solutions possible. When adding bis(2,4,4‐trimethylpentyl)acid (HR, CYANEX 301) to the HL and HA mixture, a significant synergistic effect takes place. The composition of the extracted complex with Kelex 100 was found to be [GeL3]+[R−]. The use of extraction systems based on both Kelex 100 and LIX 63, and on their mixture with CYANEX 301 in the presence of thiocyanate ion is of undoubted practical interest for hydrometallurgical processes to recover germanium..