Most analyses of natural fibers give the average composition of the fiber and not the nature and distribution of surface species present. The nature of the fiber surface is important since it governs interfacial adhesion between fiber and matrix and the transfer of stress to the fiber in composite materials. The surface of caustic treated flax fibers is analyzed using X-ray photoelectron spectroscopy (XPS) and a low voltage scanning electron microscopy (SEM) technique that uses a filtered in-lens electron detector. XPS shows that the fiber surface is not composed of a single polymer but is a mixture of materials, probably degraded lignin and hemicellulose and extractives. The SEM technique shows patches of material on the surface with different contrast and this contrast is shown to result from different average atomic number (Z). The variation in surface composition has obvious implication in variable interfacial properties in composites made using natural fibers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39572.