A–C:H (hydrogenated amorphous carbon) films were deposited by pulsed direct-current (d.c.) plasma enhanced chemical vapor deposition on silicon substrates. This study investigated the structural and mechanical evolution of the as-deposited films with fullerene-like nanostructure. The results showed that pulsed d.c. negative bias (−500 ~ −1000 V) signally influenced the growth rate, hardness, surface roughness, sp3 content, and friction behavior of the films. As the pulsed d.c. negative bias voltage increased, the sp3 content, surface roughness, hydrogen content and the friction coefficient of the films decreased; however, the growth rate and the hardness increased. The films deposited at −1000 V with fullerene-like microstructure display a nanohardness of about 19.7 GPa and the smallest friction coefficient (~0.06). The evolution on mechanical and structural properties of the films are explained by the a–C:H growth mechanism based on the interaction on plasma-surface interface and the subsurface reactions in the film. Copyright © 2014 John Wiley & Sons, Ltd.