PVOH is an unusual polymer in that it is atactic, yet crystalline. It adsorbs irreversibly from aqueous solution to hydrophobic solid in contact with the solutions. The polymer concentrates at the interface, exceeds its “kinetic solubility” in this region and crystallization ensues yielding adsorbed continuous thin films that are 10 - 50 Å thick. Crosslinking the PVOH renders it stable to hot water and does not decrease (in fact can increase) wettability. This is a versatile technique to hydrophilize hydrophobic solids and introduce alcohol functionality to surfaces. Therefore, subsequent alcohol chemistry can be carried out on these supported polymer monolayers. Waterborne coatings have been a green chemistry revolution for commodity paints, allowing users to apply protective coatings dispersed in water that are ultimately waterproof. UNH traditionally have a strong effort in this area of research and is leading the studies to characterize the orientation of chain segments as a function of thickness on various substrates. Better understanding of structure and morphology development both in the wet and dry state is desirable. The development of structure and morphology during the deposition of the PVOH is also being studied.