AbstractSurface structural characterisation of three different starch‐based blends (with poly[ethylene‐co‐(vinyl alcohol)], cellulose acetate and polycaprolactone) was carried out. The results show that there is a difference between the bulk and the surface composition of all studied blends. Two different hypotheses were investigated – predominant presence of a synthetic component on the surface and possible inter‐ and/or intramolecular bonds. The results were related to previous data for cell behaviour on those materials. It was found that both surface hydrophilicity and surface functionality are of great importance for cell adhesion and growth on starch‐based biomaterials.magnified image