Diamond-like carbon (DLC) films have low friction coefficient against variety of materials and high wear resistance; however, DLCs are often damaged when the DLC film is distorted with deformation of the substrate. Segment-structured DLC (S-DLC) coating has been developed to improve these weak points of DLC films. The S-DLC coating is a technique to separate the DLC film into the small segments. The purpose of this study is to fabricate S-DLC film on stainless steel substrate and functionalize DLC films on the substrate based on S-DLC film. In this study, fluorocarbon polymer embedded segment-structured DLC (FC-S-DLC) film was fabricated by spraying fluorocarbon polymer into the grooves between the DLC segments. The DLC films were deposited by a RF plasma chemical vapor deposition (CVD) method. Evaluations of tribological properties of these high-functional DLC films were performed under plane contact condition by pin-on-disk (PoD) test. As a result, the S-DLC film exhibited better tribological properties than that of continuous DLC film. Furthermore, the FC-S-DLC coating exhibited the most excellent tribological property among all samples and gave high wear resistance and steady friction coefficient to stainless steel substrates at a plane contact pressure of 0.16∼0.24MPa.