The chemical composition and morphology of pulp fibers have a significant impact on the properties of fiber products. Pulp samples from a novel unique Eucalyptus triple hybrid [Eucalyptus grandis × (Eucalyptus urophylla × Eucalyptus globulus)] were obtained by various pulping processes – kraft, soda-anthraquinone (NaOH-AQ), and thermomechanical pulping (TMP). The chemical composition of the fiber surfaces was evaluated by X-ray photoelectron spectroscopy (XPS). The surface lignin content of NaOH-AQ pulp fibers was lower than that of the kraft counterpart. However, kraft pulp handsheets showed better physical and mechanical properties. XPS data strongly suggests that together with the pulp bulk chemical composition the xylan is more abundant on the surface of kraft fibers, which is reflected on their better mechanical properties. Moreover, the relatively low surface lignin content in TMP pulp compared to wood suggests that defibration takes place in the secondary wall, where lignin is less concentrated.