The present investigation reports the formation of stable polyelectrolyte complexes of poly-gamma-glutamic acid (γPGA) and chitosan (Chit) by self-assembly in aqueous media at room temperature. The solubility and size of these nanoparticles in the dried and swollen states will be described and discussed. The correlation of size of particles, pH of the solutions, concentration, order of addition and the ratio of compound polyelectrolytes have been studied. It was found, that the size and size distribution of the nanosystems depends on the concentrations of γPGA and Chit solutions and their ratio as well as on the pH of the mixture and the order of addition. The diameter of individual particles was in the range of 40-285 nm measured by TEM, and the average hydrodynamic diameters were between 80-200 nm. These biodegradable, self-assembled stable nanocomplexes might be useful for several biomedical applications.