The formation of spontaneous double emulsions is a peculiar phenomenon in emulsion systems. When compared to the traditional one-step and two-step methods for preparing double emulsions, spontaneous emulsification can not only steadily load uniform water droplets into an oil phase, but can also facilitate the preparation of emulsions with higher stability. However, the limited solubility of salts, which are typically used to modify osmotic pressure, in organic oils has inhibited the viability of this method for the preparation of W/O/W double emulsions. In this paper, a redox-driven spontaneous emulsification method is developed and investigated. Instead of employing oil-soluble salts, an oxidation reaction is implemented in the oil phase, which produces cation radicals and iodide counterions to generate osmotic pressure. Additionally, amphiphilic polymer chains are harnessed as stabilizers for the newly formed W/O interfaces. Various characterization methods have been used to elucidate the mechanism of both the oxidation reaction and the spontaneous formation of double emulsions.