Nickel-rich layered-oxide materials are considered promising candidates for application as cathode material in high-energy lithium ion batteries. However, their cycling performance at high voltages and rate conditions require further improvement for the purpose of commercialization. Here, we report on the facile surface modification of nickel-rich layered oxide by chemical vapor deposition with methane which yields a conductive and protective artificial solid electrolyte interphase layer consisting of amorphous carbon, alkyl lithium carbonate, and lithium carbonate. We examine the mechanism of the protective layer formation and structural deformation of the nickel-rich layered oxide during chemical vapor deposition with methane. Via optimizing the reaction conditions, we improve the electrical conductivity as well as the interfacial stability of the nickel-rich layered oxide without inducing structural deformation. The surface-modified nickel-rich layered oxide exhibits an improved performance due to the resulting enhanced rate capability, high initial efficiency, and long cycle life at high voltage (>4.5V).