Production of chemical and oil-chemical industries on 80% is relayed to catalytic processes. It also includes liquid-phase oxidation of hydrocarbons. Despite there are a lot of scientific researches in this area, search of new catalytic systems that can improve technical and economical indicators of industrial homogeneous catalytic processes of oxidation will stay relevant for many more years. Process of liquid-phase oxidation of ethylbenzene is not only valuable industrial process, main products of which are acetophenone (AP) and hydroperoxide of ethylbenzene (HPEB), but also a model process for oxidation of alkylaromatic compounds. Due to that fact it was logical to research influence of surface-active compounds (SAC) at process of oxidation. Catalytic systems consisted from most used industrial catalysts – naftenate of cobalt (NC) and acetate of cobalt (AC), and catalytic additives. As additives were used polyethylene glycol (PEG) and hromoksan. HPEB was identified titremetrically AF and methylfenylcarbinol by chromotografy. Obtained results showed us that either ionogenic or nonionogenic SAC have significant influence on process of ethyl benzene oxidation. They are influencing not only reaction speed but products ratio as well. But however mechanism of that influence differs. Usage of PEG as catalytic additive allows to receive more HPEB in products of reaction comparing to oxidation in presence of only NC or AC. Usage of с hromoksane give us more AF