Multiphase Ti(C, O, N)/a-C:H thin filmwas synthesized by reactivemagnetron sputtering of TiC in controlled CH4, O-2 and N-2 media. The resultant chemical structure and composition of this complex phase are governed by the substrate temperature. At a lower substrate temperature of 40 degrees C, hydrogenated amorphous carbon (a-C:H) with defected aromatic sp(2) domains was dominated with titanium oxide and titanium oxynitride phases and small fraction of nanocrystalline TiCx grains was observed. With an increase in substrate temperature to 200 degrees C, carbon concentration is increased which existed in a-C:H and nanocrystalline TiCx phase while the amount of titanium, oxygen and nitrogen are decreased. Interestingly, sp(i) domains in the film were not observed at this substrate temperature. However, at substrate temperatures 300 and 400 degrees C, a-C:H and sp(2) domains are further increased but the amount of nanocrystalline TiCx phase decreased. At high temperature, the concentration of elemental titanium, carbon, oxygen and nitrogen are less due to the formation of Ti(C, O, N)/a-C:H and sp(2) cluster. Lowfriction coefficient and exceptionally highwear resistance of this film is derived fromthe existence of sp(2) domains. The absence of this phase in the film showed significantly high friction coefficient and high wear despite the presence of high amount of nanocrystalline TiCx phase. (C) 2015 Elsevier B.V. All rights reserved.