Polydimethylsiloxane (PDMS) films were prepared on silicon wafers by spin coating. The tribological properties of the PDMS films sliding against AISI-52100 steel ball were investigated with a dynamic static friction coefficient measurement apparatus in a ball-on-plate configuration. It was found that crosslinking, end grafting, and chemical characteristics of the substrate surfaces combined to play an important role in keeping the films' stability and improving the friction-reduction and wear-resistant properties. It was also noted that crosslinked PDMS films on hydroxylated substrates exhibited the most stable friction coefficient and the longest antiwear life, while a friction coefficient below 0.01 was observed for the crosslinked PDMS films on hydrophobic substrates. The latter might be attributed to the weak interaction at the interface of PDMS layer and the self-assembled monolayer. The friction coefficient appeared to be velocity dependent. At higher sliding velocities, the films showed more stable and smaller friction coefficients; this might be attributed to the shear thinning effect.