The correlation of lithium ion and other elements at the surface of the battery electrode made of polyacenic semiconductive (PAS) material film is discussed focusing on the passivation-layer formation. Behavior of these elements in the passivation layer of the Li-doped PAS films at several stages of doping were examined by the depth-profiling technique of X-ray photoelectron spectroscopy (XPS) together with the Li-doped graphite film sample for the reference. A certain different nature of the doped Li ion (Lidelta+) and carbanion (Cdelta-) between the PAS and graphite films has been revealed. It was concluded that the PAS material film possesses certain surface nanopores or nano-reaction fields to accommodate the passivation species near its surface, being completely different from the graphite film.