The diamond-like carbon (DLC) films were deposited under different deposition parameters by using arc technology. The detailed relationship of sp3 structure with the D peak of the DLC films' Raman spectra is discussed. In aid of the discussion, X-ray photoelectron spectroscopy was used to determine the DLC films' C1s binding energy. By comparing the binding energy with the Raman shift of the films, it can be found that the intensity of D peak decomposed from the Raman shift can be increased not only by the graphite cluster, but also by higher content of sp3 bonds. Higher sp3 content of DLC films can be obtained by using 90 degree magnetic filter. The study shows that the C1s binding energy of DLC films, whose Raman spectra have higher intensity of D peak, can be 284.15 or 285.50 eV, which reveals that the DLC films may have higher graphite-like or diamond-like structure, respectively.