The technology for electrostatic enhancement of coalescence of water droplets in oil emulsions is critically reviewed. Historically, the electrostatic coalescer was invented for the petroleum-related industries in California [US Patent 987 115 (1911)]. Nowadays, this technology is generally considered for the separation of an aqueous phase dispersed in a dielectric oil phase with a significantly lower dielectric constant than that of the dispersed phase. Various designs have been introduced, with most using alternating current (AC) electric fields with mains frequency (50 or 60 Hz). The direct current (DC) electric field has been less common in the past as compared to the AC. In 1981, the concept of pulsed DC electric fields was introduced, together with insulated electrodes [Trans. IChemE 59 (1981) 229-237; UK Patent 217 103 1 A (1986)]. Since then, this has become more common in the electrocoalescence technology. Pulsed DC and AC fields are especially useful, when the aqueous phase content of the emulsion is high, to prevent short-circuiting between the pair of electrodes. Processing of oil from old wells is a good example, where the volumetric water content could vary significantly. Reported work by some workers indicates the existence of an optimum frequency, which depends on the electrode coating material, its thickness and the liquid emulsion composition. This is however, a contentious issue which has not been completely resolved. The characteristics and geometry of the electrode system (generally cylindrical or plate) influence the performance of the electrostatic coalescer, and are closely related to the type of the applied electric field and the emulsion used. There are basically two types of electrode: uninsulated electrode and insulated electrode. Combination of electrocoalescence and mechanical separation (e.g., centrifugal force) has also been introduced. Heating and the addition of chemicals have been shown to further enhance the electrocoalescence of water droplets. Other methods that can be combined with the electrical treatment are filtration, methods employing high pressure and temperature, and mixing. This review paper also looks at some of the current specific industrial applications using the electrocoalescence technology. Besides the oil and petroleum industries, this technology has potential applications in the edible oil industries such as palm oil, sunflower oil and vegetable oil processing. Most of the currently available equipment is very big and bulky, having a large inventory of emulsion. Therefore, we see the future trend for new developments to be in the direction of inventing small portable devices, incorporating features such as optimum electric fields and combined electrical and centrifugal forces to further enhance the separation of water-in-oil emulsions. Furthermore, a better understanding of the fundamentals of electrocoalescence will enable a better design of the geometry of the electrodes, of the flow field with respect to the electric fields, the type of dispersion used and the type of the applied electric field.