An investigation has been made of the kinetics of oxidation of dodecane (RH) and the decomposition of dodecane hydroperoxide (ROOH) at 140 degrees C with additions of surface-active substances: alkylsulphates CnH2n+1SO4Na (C-10, C-12, C-13) and sodium bis-(2-ethylhexyl)sulphosuccinate (AOT). It was established that additions of alkylsulphates increase the thermal decomposition rate of hydroperoxides and catalyse the formation of olefins in this process. During the oxidation of dodecane in the presence of sodium dodecylsulphate (DDS), oxidative dehydrogenation with a 20% yield is also observed. AOT has no influence on the oxidation and decomposition rate of ROOH. The data obtained indicate the considerable role of the formation of aggregates of alkylsulphates of the mixed micelle type on the kinetics of oxidation of RH and the breakdown of ROOH.