Chitosan/poly(methacrylic acid) complexes, CS/PMAA, were prepared via dropwise addition of a solution of PMAA to a solution of chitosan in acetic acid 2 wt %. The increase in molecular weight of PMAA inhibited the formation of insoluble complexes, while the increase in ionic strength first favored the formation of the complex followed by inhibiting it at higher concentrations. These observations were related to a description of polyelectrolyte complexation that was strongly dependent on macromolecular dimensions, both in terms of molecular weight and of coil expansion/contraction driven by polyelectrolyte effect.