Application of various surface-active compound (SAC) in world practice of autoclave hydrometallurgy of sulphidic polymetallic materials are considered. The results of SAC check in operation of high-temperature leaching of nickel — pyrrhotine concentrates according to laboratory researches, semi-industrial and industrial tests are generalised. Requirements to the surface-active additive adequately answering to the basic processes, proceeding at autoclave oxidation of pyrrhotine are formulated. A combination of lignosulphonates and products of organic compound sulphanation are recommended to use as a sulphur de-emulsification agent for combined SAC. The specified products show high affinity to platinum metals at the oxidized pulp flotation and process intensifications of sulfur coalescence at its autoclave melt.