DLC films were deposited on Si wafer by RF plasma assisted CVD using CH4 gas. Tribological tests were conducted using rotating type ball on disk friction tester in dry air. Four kinds of mating balls were used. The mating balls were made with stainless steel but apply different annealing conditions to achieve different hardness conditions. Testing results in all load conditions showed that the harder the mating materials, the lower the friction coefficient among the three kind of martensite mating balls. In case of austenite balls, the friction coefficients were lower than fully annealed martensite ball. The high friction coefficient in soft martensite balls seems to be caused by the larger contact area between DLC film and ball. The wear tracks of DLC films and mating balls could have proven that effect. Measuring the wear track of both DLC films and mating balls have similar tendency comparing to the results of friction coefficients. Wear rate of austenite balls were also smaller than that of fully annealed martensite ball. The results of effect of applying load showed, the friction coefficients were become decrease when the applying loads exceed critical load conditions. The wear track of mating balls showed that some material transfer occurs from DLC film to mating ball during the high friction process. Raman spectra analysis showed that transferred material was a kind of graphite and contact surface of DLC film seems to undergo phase transition from carbon to graphite during the high friction process.