Xylan-coated cellulose thin films has been investigated by means of atomic force microscopy (AFM) and force mapping experiments. The birch xylan deposition on the film was performed under control by means of a multiple parameter surface plasmon resonance spectroscopy (MP-SPR) under dynamic conditions. The coated films were submitted to AFM in phase imaging mode to force mapping with modified AFM tips (sensitive to hydrophilic OH and hydrophobic CH3 groups) in order to characterize and localize the xylan on the surfaces. At the first glance, a clear difference in the adhesion force between xylan-coated areas and cellulose has been observed. However, these different adhesion forces originate from topography effects, which prevent an unambiguous identification and subsequent localization of the xylan on the cellulosic surfaces.