The efficacy of separating water-in-oil emulsions depends on the stability of the emulsion, which is influenced by the interaction of the polymer and surfactant at the oil–water interface. We examined the role of hydrolysed polyacrylamide and surfactants on the stability of water-in-oil emulsions. The effects were investigated by implementing bottle tests (BT) and electrocoalescence bottle tests (EBT) using various types of surfactants over a wide range of concentrations. For a high volume fraction (10% v/v) of emulsion, the BT study showed 80% of separation in a short duration. At a small volume fraction (2% v/v), efficient separation was achieved by applying an electric field. These studies were further extended to a hybrid mode of operation, combining 1 kV/cm, non-uniform DC electrical fields at a temperature of 60 °C, to achieve maximum separation efficiency of up to 91% within 10 min for deionised water when the volume fraction of water in the emulsion was 2%. Under the same conditions, we observed an impressive 88% separation for surfactant and polymer-stabilised emulsions. HPAM does not affect interfacial tension due to its lack of amphiphilic character. However, it significantly increases the viscosity of the dispersed phase by forming a network that restricts coalescence, thereby affecting the separation rate. Surfactants enhance stability by reducing interfacial tension (IFT) and forming a protective layer around the droplet. The findings provide valuable insights for optimising separation processes using the synergy of the heating and electric fields. The study successfully and efficiently separates oil and water, even when dealing with challenging emulsions containing polymers and surfactants, by combining heating and electrical methods.