AbstractIn the present work the morphology of high‐density polyethylene (HDPE) extrusion coating layer on high‐density paper (HDP) has been investigated. An uneven layer with a high content of crystallinity against the paper surface was discovered. The methods applied were solid‐state 13C NMR Spectroscopy and Atomic Force Microscopy. The highly crystalline layer was found to be mainly monoclinic crystallinity. The formation of the monoclinic crystallites was probably initiated by orientation of the polyethylene molecules by drawing, adhesion to the fibrous paper surface, and pressure. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 218–225, 2004