Undoped nanocrystalline diamond (NCD) films less than 1 μm thick grown on Si (100) silicon by microwave plasma-assisted chemical vapor deposition at a frequency of 2.45 GHz are studied. To obtain diamond dielectric films with maximum resistivity the deposition of films in three gas mixtures is investigated: hydrogen-methane mixture, hydrogen-methane mixture with the addition of oxygen and hydrogen-methane mixture with the addition of an inert gas. A relationship has been established between the growth conditions, structural and electrical properties of NCD films. It is shown that for the use of NCD films as effective dielectrics preliminary high-temperature annealing of the films is required, for example, in vacuum at a temperature of 600°C for one hour.