Although DLC coatings have good tribological properties, these are dependent on the deposition method, property of contact surface, and test condition. Si-DLC/DLC coatings with various Si content were deposited on Si substrates and tested using a reciprocating friction tester against steel balls. The results revealed that the tribological behavior of Si-DLC/DLC coatings was dependent on the Si content. The formation of transfer film and wear particles on the contact surface was greatly influenced by the Si content in DLC coatings. In particular, silicon oxide transfer film formed by tribochemical reaction contributed to reduce wear and friction.