The model wastewater samples investigated in the current study represented oil-in-water (O/W) emulsions with small oil (diesel/black oil) and high surfactant (Anrol/Decon90) concentrations generated during washing of oil tankers or tank-wagons. Coagulation with aluminium sulphate, ferric chloride and lime milk, and chemical oxidation by hydrogen peroxide catalyzed ferrous ions were applied as traditional and advanced treatment processes, respectively. Coagulation proved more feasible for oil content removal than for COD reduction. Both COD and oil content removal, were higher if Anrol was used as a surface active agent. The comparison of wastewater samples with different oil products but the same detergent showed more effective black oil removal. Coagulation was found ineffective as a pre-treatment technology for biodegradability improvement and toxicity reduction in surfactant stabilized O/W emulsion wastewater samples. The application of Fenton chemistry showed significant COD, UV absorbance and BOD removal, but no improvement in wastewater samples biodegradability. The maximum COD reduction and oil content removal from wastewater samples was above 90%. The oxidation of wastewater containing Decon90 required higher dosages of the Fenton reagent than wastewater with Anrol. Both Anrol and Decon90 contaminated wastewater samples were found to be detoxified even after moderate hydrogen peroxide dosages had been applied in the oxidation step.