We demonstrate the electrostatic formation of chitosan-based polyplex particles, counterbalanced by polyacrylate as an anionic polyelectrolyte. The resulting polyplex exhibited pH- and compositiondependent changes in their surface charges as measured by zeta potential, which can be employed to provide the interparticle repulsive forces for enhanced colloidal stability in homogeneous solution. Subsequently, amide coupling between the acrylates and glucosamine residues of chitosan inside the polyplex further generated the hydrogel particles, which showed the temperature-sensitive swelling property. This aspect can be attributed to the partial formation of acryl amide residues, which have been generally known to possess the lower critical solution temperature (LCST).