Applications for vanilla essential oil extracted from vanilla pods have been limited since the effective components of vanilla could be easily influenced by environmental factors, such as temperature, light, and oxygen, which hinder their effectiveness. In this study, vanilla essential oil was encapsulated in a Pickering emulsion with octenyl succinic acid starch (OSA—starch). The optimal process conditions for emulsion preparation were determined as 5% vanilla essential oil phase with 2.5% OSA—starch when they were ultrusonicated for 3 min at 470 W. Under these conditions, the minimum particle size was 0.456 μm, the oil droplets were completely encased by starch, and no new chemical bonds were formed. The smallest particle size was produced at a pH of 4 and 500 mM ion concentration. The antioxidant activity of the emulsion was greater than that of the pure vanilla oil at the same oil content. After 24 h storage, the antioxidant activity of the emulsion was enhanced, and the vanilla essential oil was slowly released in the emulsion. These results indicated that the vanilla essential oil encapsulated in a Pickering emulsion with octenyl succinic acid starch showed its tremendous potential for use in the food industry.