Biomass-derived bio-oil is a sustainable and renewable energy resource, and liquefaction is a potential conversion way to produce bio-oil. Emulsification is a physical upgrading technology, which blends immiscible liquids into a homogeneous emulsion through the addition of an emulsifier. Liquefaction bio-oil from food waste is characterized by its high pour point when compared to diesel fuel. In order to partially replace diesel fuel by liquefaction bio-oil, this study aimed to develop a method to simultaneously extract and emulsify the bio-oil using a commercial surfactant (Atlox 4914, CRODA, Snaith, UK). The solubility and stability of the emulsions at various operating conditions such as the bio-oil-to-emulsifier ratio (B/E ratio), storage temperature and duration, and co-surfactant (methanol) addition were analyzed. The results demonstrate that higher amounts of bio-oil (7 g) and emulsifier (7 g) at a B/E ratio = 1 in an emulsion have a higher solubility (66.48 wt %). When the B/E ratio was decreased from 1 to 0.556, the bio-oil solubility was enhanced by 45.79%, even though the storage duration was up to 7 days. Compared to the emulsion stored at room temperature (25 °C), its storage at 100 °C presented a higher solubility, especially at higher B/E ratios. Moreover, when methanol was added as a co-surfactant during emulsification at higher B/E ratios (0.714 to 1), it rendered better solubility (58.83–70.96 wt %). Overall, the emulsified oil showed greater stability after the extraction-emulsification process.