The use of a 50-nm thick Mo interlayer on silicon substrates for the nucleation enhancement of microcrystalline diamond (MCD) and nanocrystalline diamond (NCD) films synthesized by hot filament chemical vapour deposition was studied. The MCD and NCD films were deposited using methane concentrations of 1% and 2%, respectively. The presence of a Mo nucleation layer enabled the formation of more uniform NCD films with reduced surface roughness (rms roughness approximately 40 nm for a 750-nm thick layer) and with significantly less interfacial voids due to the superior nucleation densities and surface coverage in the early stages of NCD film formation. During the initial stages of MCD film growth, the nucleation density increased by one order of magnitude as compared to uncoated silicon. As a result, much thinner MCD films with smaller surface grain sizes and, thus, reduced surface roughness could be produced as well. The presence of a Mo nucleation layer not only leads to a structural optimization of NCD and MCD films but also allows fast nucleation and film growth kinetics at relatively low substrate temperatures (approximately 575 degrees C), relevant for the coating of substrate materials that do not withstand high substrate temperatures.