Environmentally friendly and outstanding pH responsiveness cationic starch nanoparticles (CSNP) were prepared through ethanol precipitation from pH-sensitive starch, which preparation of cationic starch (CS) by grafting copolymerization with dimethylaminoethyl methacrylate (DMAEMA). In this work, CSNP showed a nanometer size and regular sphere, highly free-flowing molecular chains, and outstanding pH responsiveness which was proved by the high stability of its stabilized emulsion through 6 emulsification/ demulsification transition. The result of the SEM and particle size distribution indicated that the size of the CSNP-0 was about 800 nm, and decreased with the DMAEMA increased. Moreover, the CSNP-stabilized emulsion was stable at pH = 7 and pH = 12. However, this emulsion exhibited breakage at pH = 2. In addition, the CSNP-stabilized Pickering emulsion achieved an emulsification/demulsification switching by cycling the pH at least 6 times, during which the average droplet size gradually increased. At pH ≥ 7, the emulsions exhibit shear thinning behavior.