We study biosourced core-shell particles with a starch-based core and thermo-responsive polymer brush shell using surface-initiated single-electron transfer living radical polymerization (SI-SET-LRP) as a Pickering stabilizer. The shell endows the Pickering stabilizer with reversible emulsification/demulsification of oil and water properties. The initiator attached to the starch-based nanosphere (Br-SNP) core particle was first fabricated using the precipitation method. Subsequently, dense poly(N-isopropylacrylamide) (PNIPAM) brush graft-modified starch-based nanoparticles (SNP-g-PNIPAM) were obtained via the SI-SET-LRP process. Interfacial properties of the resultant particles were analyzed by interfacial tensiometer measurements, as were the effects of the grafted polymer chain length and temperature on the interfacial activity. Pickering emulsion was obtained using SNP-g-PNIPAM particles as the stabilizer. The effect of the concentration of the Pickering stabilizer on the size of emulsion droplets was analyzed. The emulsification/demulsification process of the Pickering emulsion can be reversed and easily repeated by changing the temperature.