This work presents the procedures for monitoring volatile organic compounds during treatment of industrial effluents. The investigation was carried out for a specific effluent caustic effluent from bitumen production. The developed procedures enable more detailed control of the effectiveness of wastewater treatment than standard procedures. Caustic effluents from bitumen production have a complex physicochemical form and consist of an emulsion of an organic phase in a strongly alkaline aqueous phase. The occurrence of an emulsified organic phase in the aqueous phase of the effluents results in their high toxicity toward the activated sludge of a refinery wastewater treatment plant as well as strong malodorousness. Interpretation of analytical results reveals that the effluents contain over 400 organic compounds among volatile organic compounds (VOCs) alone. Using the developed procedures, 114 of the VOCs were identified in raw postoxidative effluents. The procedures described in this work allow detailed identification of VOCs as well as the determination of distribution of their concentrations for individual classes of chemical compounds. Monitoring changes in content of individual classes of VOCs, including highly malodorous volatile sulfur compounds, as well as changes in total VOC content, provides more information on the processes taking place during wastewater treatment.