We describe the preparation and characterization of a green and renewable polyelectrolyte complex (PEC) containing phosphorus, nitrogen and carbon elements, based on the ionic complexation between chitosan and phytic acid. Introduction of this PEC to ethylenevinyl acetate copolymer (EVA) leads to an improvement of the flame retardancy. As for the EVA/PEC composites with 20.0 wt % of PEC (EVA/20PEC), the char residue at 600 degrees C is 12 wt % higher than that of the pristine EVA under nitrogen atmosphere. Compared to the pristine EVA, the peak heat release rate and total heat release of EVA/20PEC show 249 W g(-1) and 5.6 kJ g(-1) decreases, respectively. The char residue of EVA/20PEC is full and compact, demonstrating excellent intumescent effect. Introduction of this PEC also contributes to a slight increase of the Youngs modulus while maintains the excellent ductility. This work provides a new approach for the development of environmentally friendly intumescent flame retardant system.