One-step double emulsions via only one-step emulsification are leading to an attractive branch of emulsion research studies owing to the ease of preparation and reduced surfactant numbers. In addition to controlling the oil/water ratio, exploiting emulsifiers with desirable amphiphilicity that can stabilize both the inner and outer water/oil interfaces is crucial to the formation of one-step double emulsions. In particular, new emulsifiers with saving laborious efforts are highly preferred in consideration of low cost and practical applications. In this work, a commonly used homopolymer, polyethylene glycol (PEG), was attempted as emulsifiers to prepare emulsions via one-step emulsification. PEG is generally considered as a hydrophilic polymer and always anchored with a hydrophobic polymer to make the copolymer amphiphilic. In the waterchloroform binary system, PEG itself exhibits amphiphilic performance and tailors the formation of single emulsions or double W/O/W emulsions on the dependence of the oil/water ratio and the PEG concentration. A possible mechanism as explained by dissipative particle dynamics simulation was proposed to demonstrate the amphiphilic feature and emulsification capability of PEG. The amphiphilicity of PEG was further tuned by interacting with iodine as a result of the formation of a supramolecular complex, which, in turn, led to the conversion from single emulsions to O/W/O double emulsions. It is believed that this line of research provides inspiration for the preparation of controllable emulsions through supramolecular routes.