In this work, nanoparticles were prepared by the composite of cationic starch (CS) and xanthan gum (XG) through gelatinization and alcohol precipitation for the first time. Physicochemical properties, micromorphology, and emulsification properties of CS/XG nanoparticles were measured. SEM showed that after compositing with XG, the diameter size of the CS/XG nanoparticles was increased from about 50 nm to 150-300 nm. FT-IR, XRD and 13C CP/MAS NMR confirmed that XG was successfully complexed with CS. Besides, the visual observation indicated emulsions stabilized by CS/XG nanoparticles had excellent storage and thermal properties. Additionally, the rheological and stability results of emulsions show that pH and NaCl had effects on the rheological and stability properties of emulsions, which means that the prepared emulsions had environmental responsiveness. Thus, this work provides an efficient method to prepare CS and GX composite nanoparticles with efficient emulsifying properties.