Diamond, having many advanced physical and mechanical properties, is one of the most important materials used in the mechanical, telecommunication and optoelectronic industry. However, high hardness value and extreme brittleness have made diamond extremely difficult to be machined by conventional mechanical grinding and polishing. In the present study, the microwave CVD method was employed to produce epitaxial diamond films on silicon single crystal. Laser ablation experiments were then conducted on the obtained diamond films. The underlying material removal mechanisms, microstructure of the machined surface and related machining conditions were also investigated. It was found that during the laser ablation, peaks of the diamond grains were removed mainly by the photo-thermal effects introduced by excimer laser. The diamond structures of the protruded diamond grains were transformed by the laser photonic energy into graphite, amorphous diamond and amorphous carbon which were removed by the subsequent laser shots. As the protruding peaks gradually removed from the surface the removal rate decreased. Surface roughness (Ra) was improved from above 1μm to around 0.1μm in few minutes time in this study. However, a scanning technique would be required if a large area was to be polished by laser and, as a consequence, it could be very time consuming.