Hydrogenated amorphous carbon films codoped with Si and Al ((Si, Al)/a-C:H) were deposited through radio frequency (RF, 13.56 MHz) magnetron sputtering on Si (100) substrate at different temperatures. The composition and structure of the films were investigated by means of X-ray photoelectron spectroscopy (XPS), TEM, and Raman spectra, respectively. The substrate temperature effect on microstructure and mechanical and tribological properties of the films was studied. A structural transition of the films from nanoparticle containing to fullerene-like was observed. Correspondingly, the mechanical properties of the films also had obvious transition. The tribological results in ambient air showed that high substrate temperature (>573 K) was disadvantage of wear resistance of the films albeit in favor of formation of ordering carbon clusters. Particularly, the film deposited at temperature of 423 K had an ultralow friction coefficient of about 0.01 and high wear resistance.