In this study, the effect of grain boundary on the frictional behavior under the oil-lubricated condition was investigated by varying the grain size (crystallite size) of the pure Fe samples prepared via physical vapor deposition. A high fraction of grain boundary in the sample yielded a low friction coefficient mu in the case of a lubrication oil that formed a chemisorbed film on the surface of the material. Thick absorbed layer formed on the surface was observed only in the sample with high fraction of grain boundary. These results indicate that a disordered structure in the vicinity of grain boundary preferentially forms chemisorbed films and reduces mu by protecting the surface of the material.