Catalyst passivation through carbon poisoning is a common and costly problem as it reduces the lifetime and performance of the catalyst. Adding oxygen to the feed stream could reduce poisoning but may also affect the activity negatively. We have studied the dehydrogenation, decomposition, and desorption of naphthalene co-adsorbed with oxygen on Ni(111) by combining temperature-programmed desorption (TPD), sum frequency generation spectroscopy (SFG), photoelectron spectroscopy (PES), and density functional theory (DFT). Chemisorbed oxygen reduces the sticking of naphthalene and shifts H2 production and desorption to higher temperatures by blocking active Ni sites. Oxygen increases the production of CO and reduces carbon residues on the surface. Chemisorbed oxygen is readily removed when naphthalene is decomposed. Oxide passivates the surface and reduces the sticking coefficient. But it also increases the production of CO dramatically and reduces the carbon residues. Ni2O3 is more active than NiO.