Using membrane materials to purify viscous watery oil from industrial production processes and accidental oil spills is of great importance but still challenging. Based on the excellent electrical conductivity and electric-thermal conversion of poly(pyrrole) (PPy), a hydrophobic PPy-modified micro-fibrillated cellulose membrane (P-CP) was successfully prepared. The size of the P-CP membrane can be customized to meet specific requirements. In this research, the membrane diameter is capable of reaching 24 cm. By applying a voltage ranging from 0 to 12 V, the surface temperature of the P-CP membrane can be elevated to roughly 120 °C. After 10 cycles of heating and cooling under 12 V voltage, the electric-thermal curves, surface hydrophobicity, and pore structure of P-CP membrane can remain stable, which suggests remarkable electric-thermal stability and reliability despite prolonged operation. The P-CP membrane shows good linearity between voltage and current (R2 = 0.997) and easy temperature control from room temperature to ∼120 °C at low supply voltage (0–12 V). Under the condition of 12 V power supply and self-gravity, the separation flux of the P-CP membrane for water-in-oil (W/O) emulsions (kerosene, diesel) is 2–3 times higher than that at room temperature, and the separation efficiency is also improved. Importantly, the P-CP membrane shows excellent separation performance for high viscosity water-in-crude oil emulsions, with a separation flux of 40 L m–2 h–1 by gravity. Compared to the situation without electricity, the separation flux of water-in-crude oil emulsion has increased four-fold. The joule heating of the P-CP membrane expands its service time and application scenarios, demonstrating its great application prospects in actual viscous oil–water emulsion separation.