We investigate the plasticizing effect of salt and water on hydrated polyelectrolyte assemblies via molecular dynamics simulations corroborated by connected by experimental modulated differential scanning calorimetry(MDSC)characterization of complexes formed by poly(sodium 4-styrenesulfonate)(PSS)and poly(diallyldimethylammonium chloride)(PDAC)under varying hydration and excess salt(NaCl)conditions.