The formation of colloids based on polyelectrolyte complexes (PECs) of biopolymers was investigated through the complexation between two charged polysaccharides, chitosan as polycation, and dextran sulfate as polyanion. The slow dropwise addition of components, generally used for the formation of PECs, allowed to elaborate both cationic or anionic particles with an excess of chitosan or dextran sulfate, respectively. The PEC particles featured a core/shell structure, the hydrophobic core resulting from the segregation of complexed segments whereas excess component in the outer shell ensured the colloidal stabilization against further coagulation. Considering the host/guest concept for the formation of PECs, the influence of the molecular weight of components on particles sizes could be well explained by the chain length ratios of the two polymers. As an irreversible flocculation occurred with a dropwise approach for both cationic and anionic PEC particles when the mixing ratio was close to unity, a more versatile, and simpler to setup, method was designed: the one-shot addition of one solution to the other. Because process of addition is faster than the flocculation, cationic or anionic particles could be elaborated irrespective of the order of addition of the reactant. Characterization of these particles by quasielastic light scattering, electrophoresis, and scanning electron microscopy revealed very similar properties to those obtained by a slow dropwise approach. Critical coagulation concentrations of 0.12 and 0.09 M (with sodium chloride) for cationic and anionic particles evidenced a mostly electrostatic stabilization.