This study focused on mechanistic understanding of the effect of charge ratio, order of addition and resulting thermodynamics of interaction on the formation and properties of polyelectrolyte complexes (PECs) from sodium alginate and chitosan at a constant tightly controlled pH 4 where the zeta potential difference was maximum for the formation of PECs. The morphology, particle size and particle size distribution as well as the stability of PECs were investigated as a function of molar charge ratio, and the order of addition. The association binding constant K-a and the stoichiometry of interaction between the two electrolytes, evaluated using Isothermal titration calorimetry, showed that the stoichiometry and enthalpy of reactions were strongly affected by the order of addition and influenced the average particle size and zeta potential of PECs. The addition of alginate (-) into chitosan ( + ) gave positively charged particles and resulted in stronger interactions characterized by larger enthalpy and entropy of complexation which led to smaller particles. Reversing the order of addition gave negatively charged particles that were larger. Morphologies of complexes studied using scanning electron microscopy (SEM) showed distorted spherical particles for both orders of addition and at most charge ratios. Stability during 8 weeks was found to depend on the order of addition and charge ratio. Alginate in chitosan gave more stable PECs consistent with the thermodynamics of interaction which showed stronger interactions for this order of addition. The particle sizes and size distributions rapidly increased near electrical neutrality during storage at 4 degrees C where aggregation was facilitated because of electrical neutrality but particles were stable when the net charge was either strongly positive or strongly negative.