The effects of pH, ionic strength and polymer ratio in the complexation of chitosan (CHI) with different anionic polysaccharides, namely gum Arabic (GA), sodium alginate (ALG) and kappa-carrageenan (CRG), were investigated. This was made using titration techniques, which allowed the determination of stoichiometry and binding constant of complexes. The sulfated polysaccharide interacted more strongly with CHI than carboxylated polysaccharides. The increase of ionic strength (0-100 mM NaCl) in the polysaccharides complexation resulted in a significant reduction in the binding constant of GA:CHI and CRG:CHI, but did not influence the complexation of ALG with CHI. The pH and polymer ratio affected the formation and solubility of complexes GA:CHI, while for ALG:CHI and CRG:CHI, insoluble complexes were observed in all pH and polymer ratio evaluated. A phase transition of coacervate to gel was proposed to ALG:CHI and CRG:CHI, which can be related to the self-association of anionic polymers, when these are in excess.