Three different XPS methods based on the O/C atomic ratio, C1 carbon content, and Hg amount are compared in this study to quantify the surface coverage of various pulp fiber surfaces by lignin and extractives. The sensitivity of the methods to drying technique and the stability of organically bound mercury when subjected to X-ray irradiation were also investigated. Results reveal that the surfaces of all pulp fibers have a higher content of lignin and extractives than the bulk of the fibers. Similar lignin surface coverage was obtained for thermomechanical pulp fibers using the Hg, O/C, and C1 carbon methods, while the Hg method gave lower values for kraft pulp fibers than the O/C and C1 carbon methods. The O/C and C1 carbon methods are sensitive to the drying technique, i.e., air-dried samples showed a higher amount of lignin on the fiber surface than freeze-dried samples, while no or only minor differences in results were obtained using the Hg method. The Hg method was more reproducible than the other methods. Special care must be exercised during XPS analysis to minimize mercury degradation.