Cationic and anionic starch nanoparticles were obtained by aqueous polyelectrolyte complex formation between cationic quaternary ammonium substituted starch and anionic sodium tripolyphosphate as well as anionic hydroxyethyl starch and cationic poly(dialyldimethylamonium chloride), respectively. The formation of nanosized starch particles of a spherical shape was verified by dynamic light scattering, scanning electron microscopy and atomic force microscopy measurements. The cationic starch nanoparticles of different constitution and containing various contents of quaternary ammonium groups were produced and their zeta potential was modulated between +4 mV and +14 mV by varying polycation / polyanion ratio. Negatively charged starch nanoparticles of different constitution and containing various contents of carboxyl groups were produced and their zeta potential was modulated between –3 mV and –11 mV by varying polyanion / polycation ratio. Moreover, aqueous dispersions of cationic starch nanoparticles were stable for 2–12 days at the room temperature and the stability at 4 °C was 3–22 days. Meanwhile, aqueous dispersions of anionic starch nanoparticles were stable for 3–8 days at the room temperature and the stability at 4 °C was 6–10 days.

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