The water content in multilayers made from poly(styrenesulfonate) and poly(diallyldimethylammonium chloride) was determined using infrared spectroscopy and thermal gravimetric analysis. Under ambient conditions the polyelectrolyte multilayer contains 10-20 wt % water, which is removed by heating under dry conditions to 100 degrees C. FTIR comparison of multilayers with solution-precipitated polyelectrolyte complexes of the same polymers revealed that both the composition and sulfonate group environment were identical.