Nanocrystalline diamond (NCD) has been grown on oxide coated silicon wafers by microwave plasma assisted chemical vapour deposition using a novel seeding technique followed by optimised growth conditions, and leads to a highly-dense form of this material with grain sizes around 100nm for films approximately 1.5 microns thick. The electrical properties of these films have been investigated using Impedance Spectroscopy, which enables the contributions from sources characterised by differing capacitances, such as grain boundaries and grain interiors, to be isolated. After an initial acid clean the electrical properties of the film are not stable, and both grain boundaries and grains themselves contribute to the frequency dependant impedance values recorded. However, following mild oxidation grain boundary conduction is completely removed and the films become highly resistive (>1013 ohm/sq). This is most unusual, as conduction through NCD material is more normally dominated by grain boundary effects. Interestingly, the AC properties of these films are also excellent with a dielectric loss value (tan δ) as low as 0.002 for frequencies up to 10MHz. The dielectric properties of these NCD films are therefore as good as high quality free-standing (large grain) polycrystalline diamond films, and not too dissimilar to single crystal diamond, and are therefore ideally suited to future 'silicon-on-diamond' applications.