Pulsed laser vaporization of graphite is rapidly emerging as an effective technique for the preparation of high quality diamond‐like carbon films. However, the dynamics of the process and mechanisms by which diamond‐like properties are obtained have not been well understood. The characteristics of the vapor plume generated by 248 nm KrF excimer laser irradiation of a graphite target are investigated using laser induced fluorescence and a Langmuir probe. It is found that the kinetic energy of the C2molecule increases with laser fluence, reaching a value in excess of 12 eV in the moderate fluence range (3–5 J/cm2) employed for deposition. The Cn+ions are 5–10 times more energetic and comprise ∼10% of the vapor flux. A notable finding is that irradiation of the surface at an angle of 70° with respect to the target normal increases the ion velocity when compared with 0° laser incidence at the same surface fluence. Analysis of the films prepared under such conditions supports the theory that diamond‐like film character is directly related to the kinetic energy of the depositing species.