Viscous aqueous solutions of chitosan and polyvinyl alcohol (PVA) were blended to enhance miscibility and avoid polymer phase separation. The mixtures were drop-casted and air dried to yield composite film materials that were characterized by equilibrium water uptake, physical stability in aqueous solution, and thermal stability. Chitosan/PVA blends have greater thermal stability, unique morphology, and reduced solubility in acidic solution, thus extending the useful pH range for chitosan as a sorbent material. The uptake properties of the films was investigated using methylene blue (MB) and a p-nitrophenol (PNP) dyes, where it was found that each single component polymer has greater uptake toward MB than PNP. A direct relationship between film composition (chitosan:PVA) with solution pH and the uptake of MB was observed. The results are in agreement with electrostatic interactions and contributions due to the hydrophobic effect for such composite materials.