Mass-transfer-induced multistep phase separation was found in emulsion droplets. The agent system consists of a monomer (ethoxylated trimethylolpropane triacrylate, ETPTA), an oligomer (polyethylene glycol diacrylate, PEGDA 700), and water. The PEGDA in the separated layers offered partial miscibility of all the components throughout the multistep phase-separation procedure, which was terminated by the depletion of PEGDA in the outermost layer. The number of separated portions was determined by the initial PEGDA content, and the initial droplet size influenced the mass-transfer process and consequently determined the sizes of the separated layers. The resultant multilayered emulsions were demonstrated to offer an orderly temperature-responsive release of the inner cores. Moreover, the emulsion droplets can be readily solidified into onionlike microspheres by ultraviolet light curing, providing a new strategy in designing particle structures.