We propose a new path for preparing nanostructured carbon films (NCFs) by using electron cyclotron resonance (ECR) plasma sputtering with ion–electron hybrid irradiation for controlling the frictional behavior. The frictional behavior of the NCF was measured by using a pin-on-disk tribometer with a nanoprobe displacement sensor, and the transition curves of the friction coefficient and microdisplacement of the NCFs were examined. The friction mechanism was discussed by transmission electron microscopy (TEM) observation on the wear track. From the results, we found a new method to prepare NCFs, which has the potential to achieve low friction at the early stage of sliding contact. In addition, the technology of ECR plasma with ion–electron hybrid irradiation provides a new vision to rebuild a nanostructured surface from an original surface for controlling the frictional behavior.