Steam Assisted Gravity Drainage (SAGD), the in-situ technology most widely used for bitumen extraction in Canada, produces bitumen accompanied by water in the form of a water-in-bitumen emulsion. This emulsion is particularly challenging to treat (break) due to its high viscosity and the presence of solids and natural surfactants that act as stabilizers that form an interfacial film that prevents the coalescence of the water droplets. The use of additives or temperature (or a combination of both) is a common practice to break the SAGD emulsion. However, the use of these approaches presents disadvantages such as high cost, safety, significant energy consumption, and, in the case of some additives, environmental challenges. In addition, due to the complexity of the SAGD emulsion, the demulsification performance is often low. This work proposes the treatment of stable emulsions produced in the field after in situ bitumen extraction (SAGD), by combining organic solvents and ultrasound irradiation. The experimental results of this study show that when solvents are combined with the short-time irradiation of ultrasound, the demulsification efficiency increases significantly, indicating a synergy between these two treatment strategies. The optimized treatment resulted in a high-performance, fast treatment compared to either method alone, with the added benefit of utilizing some environmentally friendly solvents. The experimental work was designed to investigate the impact of the treatments (solvent addition, ultrasound, and a combination of both) on the demulsification efficiency. The solvents were selected based on their solubility properties in water and/or bitumen. A synergic effect on the demulsification efficiency (DE) was observed for all 14 solvents tested when combined with ultrasound energy. Out of all the solvents, mutually soluble solvents, including ethyl acetate, tetrahydrofuran, diethyl ether, and pyrrolidine, showed the highest DE when combined with ultrasound. For example, a remarkable synergy (88% DE) occurred with a combination of 0.6 m (5 wt%) ethyl acetate and 15 min ultrasound, while negligible demulsification was observed when ethyl acetate or ultrasound was tested individually. This study demonstrates the synergy between solvents and ultrasonication to treat the SAGD emulsion. The use of mutual soluble solvents in emulsion treatment was also demonstrated in this work for the first time. This combination of techniques contributes to developing a highly efficient demulsification process with potentially low environmental impact.