Differences in surface chemical composition were found when examining poly(vinylacetate-co-vinylalcohol) (PVOH) film surfaces. The content of the acetate groups increased at the outermost surface when dried in air and similar content, when dried against a glass surface, compared to the bulk content. The enrichment varied from 200–1300%, as compared to the bulk content. The enrichment of the acetate groups was studied with X-ray photo electron spectrocopy (XPS or ESCA) at different analyzing angles. The bulk content was measured with Nuclear Magnetic Resonance spectrometry (NMR). © 1993 John Wiley & Sons, Inc.