In this study, we go into the examination and the discussion of the possible use of myoglobin (Mb) and hemoglobin (Hb) embedded in surfactant films of didodecyldimethylammonium bromide (DDAB) as potential materials for the effective electrochemical activation and detection of several organohalides (trichloroacetic acid (TCA), ethylene dibromide (EDB), tetrachloroethylene (PCE), trichloroethylene (TCE), dichloroacetic acid (DCA) etc.), in aqueous solution. Our descriptive results of the electrocatalytic behavior of DDAB/Mb and DDAB/Hb films constitute the first important step in the investigation of the evaluation of a strategy materializing the use of these heme-based enzymes for the detection of various significant organohalide derivatives. Limitations relative to the design of a suitable electrochemical sensor of organohalide pollutants are also discussed.