Fluorine-containing fullerene-like carbon (F-FLC) films were prepared by high frequency unipolar pulse plasma-enhanced chemical vapor deposition. The microstructures, mechanical properties as well as the tribological properties of the films were investigated. The results indicate that fullerene-like microstructures appear in amorphous carbon matrix and increase greatly with the increase of bias voltage from −600 to −1600 V. And the fluorine contents in F-FLC films also show a minor rise. In addition, the hardness enhances with the bias voltage and the outstanding elastic recovery maintains because of the formation of fullerene-like microstructures in the F-FLC films. Undoubtedly, the F-FLC film deposited under high bias voltage owns a superiorly low friction, which combines the merits of fluorinated carbon film and fullerene-like carbon film. Moreover, the film also shows a remarkable wear resistance, which is mainly attributed to the excellent mechanical properties. This study provides new insights for us to prepare fluorine-containing FLC films with good mechanical and tribological properties.