Titanium nitride (TiN) hard protective films were fabricated on AISI52100 bearing steel surface employing plasma immersion ion implantation and deposition (PIIID) technique. The TiN films were characterized using a variety of test methods. Atomic force microscope (AFM) revealed that the titanium nitride film has extremely smooth surface, very high uniformity and efficiency of space filling over large areas. X-ray diffraction (XRD) result indicated that （200） crystal face of titanium nitride phase is the preferred orientation and three kinds of titanium components exist in the surface modified layer. Tailor fitting analysis of X-ray photoelectron spectroscopy (XPS) combined with Ar ion etching proved that Ti2p1/2 and Ti2p3/2 have two peaks in the titanium nitride film layer, respectively. It is shown that different chemical state exists in titanium compound. N(1s) bond energy of XPS has also three fitting peaks at 396.51, 397.22 and 399.01 eV, corresponding to the nitrogen atom in TiNxOy， TiN and N—N, respectively. Combined with the XPS Tailor fitting analysis results of O(1s) bond energy, it was shown that there is a large amount of titanium nitride phase in addition to a small amount of simple substance nitrogen and oxide of titanium in the surface layer. The whole film system is made up of TiN, TiO2, N—N and Ti—O—N compound.