The Fe-coating and H2-annealed processes markedly increased the conductivity and enhanced the surface electron field emission (s-EFE) properties for the diamondfilms. The enhancement on the s-EFE properties for the diamondfilms is presumably owing to the formation of nano-graphite clusters on the surface of the films via the Fe-to-diamond interaction. However, the extent of enhancement varied with the granular structure of the diamondfilms. For the microcrystalline (MCD)films, the s-EFE process can be turned on at (E0)MCD = 1.9 V/μm, achieving a large s-EFE current density of (Je)MCD = 315 μA/cm2 at an applied field of 8.8 V/μm. These s-EFE properties are markedly better than those for Fe-coated/annealed ultrananocrystalline diamond(UNCD)films with (E0)UNCD = 2.0 V/μm and (Je)UNCD = 120 μA/cm2. The transmission electron microscopy showed that the nano-graphite clusters formed an interconnected network for MCDfilms that facilitated the electron transport more markedly, as compared with the isolated nano-graphitic clusters formed at the surface of the UNCDfilms. Therefore, the Fe-coating/annealing processes improved the s-EFE properties for the MCDfilms more markedly than that for the UNCDfilms. The understanding on the distribution of the nano-clusters is of critical importance in elucidating the authentic factor that influences the s-EFE properties of the diamondfilms. Such an understanding is possible only through the 3D-tomographic investigations.