Organic chlorine compounds can be persistent environmental contaminants and may be accumulated through the food chain to the aquatic organisms, to fish and humans, depending basically on their hydrophobic properties. Consequently, there is an interest to measure these organic compounds from both the scientific and regulatory communities. The analytical essays have been improved for measuring specific organic chlorine compounds that present the most toxicological potential (polychlorinated biphenyls [PCBs], certain pesticides and dioxins), although they are tedious and time-consuming procedures. The existing tests to measure adsorbable organic halogens (AOX) or extractable organic halogens (EOX) do not distinguish the more hydrophobic organic chlorine matter. The intention of this paper is to make a review of the existing methods to measure the potentially bioaccumulating organochlorine compounds (OCs) from wastewater and propose a methodology to a standardisation procedure for complex mixtures of OCs in wastewater, such as pulp mill effluents. A new method has been proposed for determining the most hydrophobic part of the extractable organic halogens (EOX(fob)), the lowest reported value is 0.6 microg/l, expressed as chloride, and the relative standard deviation at 20 microg/l is 7% on laboratory samples and 30% on real effluents. This new procedure could be a valuable tool to complement environmental risk assessment studies of wastewater discharges.