Polycomplexes of poly(itaconic acid) have been synthesized in the presence of small amounts of chitosan (eq. NH2/eq. COOH between 0 and 1.31%). We have studied the effect on the yield and polydispersity of the final materials when increasing quantities of chitosan are employed. Under the reported experimental conditions, we have found that chitosan is quantitatively incorporated into the new material to produce dramatic effects on the system behavior. It has been established a critical R-value beyond which a hidrogel is obtained. The electrostatic interactions between polyelectrolytes turn from irreversible to reversible when pH is made strongly basic.