By spectrophotometric method the complex formation of germanium(IV)  with 2,2',3,4-tetrahydroxy-3'-sulfochloroazobenzol-5' (R) with the cationic surfactants – cetylpyridiniumbromide (CPBr), cetylpyridiniumchloride (CPCl), cetyltrimethylammonium bromide (CTMABr) and decomethoxine (DEC) has been investigated. It has been established that surfactants with the reagent form a stable ion associates. Germanium in the presence of surfactants produces colored ternary complexes with a ratio of Ge(IV):R:SAS=1:2:2. The effect of pH, time, temperature and concentration of the reactants on the formation of mixed-ligand complexes has been studied. There have been developed high-quality methods for photometric determination of microquantities of germanium in natural objects.