Electrochemically-assisted technologies can be successfully applied to the treatment of oil-in-water (O/W) emulsions. In this work, it is studied the influence of the main parameters (electrical charge passed, pH, electrolyte, oil content and operation mode) in the efficiency of these processes, when aluminium electrodes are used. The pH was found to be the most significant parameter, and good removal efficiencies were only obtained for pHs in the range 5-9. The electrical charge passed was observed to be directly related to the aluminium supplied to the waste. For a given oil concentration it is required that a minimum electrical charge is passed to break-up the emulsion. Further increases in the electrical charge lead to increase in the COD removal. The influence of the oil concentration is related to that of the electrical charge passed: for a given dose of aluminium, the higher the oil content the lower the COD-removal efficiency. Likewise, to produce the break-up of the emulsion it is required a minimum dose of aluminium (electrical charge passed), lower doses do not attain the rupture of the emulsion. The type of electrolyte and its concentration were also found to influence the process efficiency. Better efficiencies were obtained in the treatment of chloride-containing wastes and for low concentration of electrolyte. The destabilization of the O/W emulsion was found to be favoured in the discontinuous operation mode. Bridging flocculation is a primary destabilization mechanism that can explain the experimental results obtained in this work.