Specific enzymes hydrolyzing pulp carbohydrates can be used for characterization of pulp fibres. By combining enzymatic peeling of fibre hemicelluloses with novel techniques of surface analysis, such as ESCA, new information can be obtained on the location of different components, i.e. xylan, glucomannan and lignin on the fibre surfaces. In this work unbleached kraft pulps were selectively peeled with purified Trichoderma reesei xylanase and mannanase and the structural modifications caused by the removal of the hemicelluloses were analyzed with ESCA. The removal of the accessible portion of the pine kraft xylan increased the amount of surface lignin, whereas mannan removal had no effect on the amount of lignin on the surface. In the case of birch kraft pulp the removal of accessible xylan did not enhance the amount of lignin on the surface. However, in birch kraft pulp the removal of xylan decreased the amount of extractives covering the surface.