Ultrasmooth nanostructured diamond (USND) films were synthesized on Ti-6Al-4V medical grade substrates by adding helium in H2/CH4/N2 plasma and changing the N2/CH4 gas flow from 0 to 0.6. We were able to deposit diamond films as smooth as 6 nm (root-mean-square), as measured by an atomic force microscopy (AFM) scan area of 2 μm2. Grain size was 4-5 nm at 71% He in (H2 + He) and N2/CH4 gas flow ratio of 0.4 without deteriorating the hardness (∼50-60 GPa). The characterization of the films was performed with AFM, scanning electron microscopy, x-ray diffraction (XRD), Raman spectroscopy, and nanoindentation techniques. XRD and Raman results showed the nanocrystalline nature of the diamond films. The plasma species during deposition were monitored by optical emission spectroscopy. With increasing N2/CH4 feedgas ratio (CH4 was fixed) in He/H2/CH4/N2 plasma, a substantial increase of CN radical (normalized by Balmer Hα line) was observed along with a drop in surface roughness up to a critical N2/CH4 ratio of 0.4. The CN radical concentration in the plasma was thus correlated to the formation of ultrasmooth nanostructured diamond films. © 2006 Materials Research Society.