Using Hall ion source assisted MF twin targets unbalanced magnetron sputtering, series of Ti/TiN, Ti/TiN/Ti(C,N) and Ti/TiN/Ti(C,N)/TiC hard anti-wear films are deposited on different materials like stainless and high speed steels by changing atmosphere, bias mode, sputtering and ion beam assisted currents. The color, crystal structure, hardness and binding force of film are tested and analyzed, respectively. Experimental results show that color of film is sensitive to atmosphere, slight change of atmosphere can influence the coating’s color seriously. The preferred orientation of Ti(C,N) films prepared by MF twin targets unbalanced magnetron sputtering has no obvious change compared with the film deposited by other PVD technologies. The substrate material has great influence on film’s hardness, binding energy and surface modification. The application of Hall current can effectively improve the binding force between film and substrate.