A heterojunction between thin films of nanocrystalline diamond (NCD) and 4H-SiC has been developed. Undoped and B-doped NCDs were deposited on both n- and p- SiC epilayers. I-V measurements on p+ NCD/n- SiC indicated Schottky rectifying behavior with a turn-on voltage of around 0.2 V. The current increased over eight orders of magnitude with an ideality factor of 1.17 at 30 °C. Ideal energy-band diagrams suggested a possible conduction mechanism for electron transport from the SiC conduction band to either the valence band or acceptor level of the NCD film. Applications as an UV semitransparent electrical contact to 4H-SiC are discussed.