AbstractThe structure and the nano‐friction behaviour of a new kind of ultrathin film, a molecular deposition (MD) film, on an Au substrate were studied. The MD film is formed by the electrostatic attraction between opposite charges of cationic and anionic compounds, and a multilayer film can be built through alternating deposition of bipolar cationic and anionic compounds. Monolayer, bilayer, trilayer, and tetralayer MD films on Au substrates were examined. MD films with an alkyl terminal group were also investigated. It was found that while the MD film on an Au substrate reduced the friction, its nano‐friction behaviour was unstable because of the active terminal group. However, if the MD film was formed with an alkyl terminal group, its nano‐friction behaviour became stable and its friction decreased markedly. Therefore, this film termination method could contribute to the nano‐tribological application of M