The synthesis of nanocrystalline diamond film on polycrystalline molybdenum substrates was carried out by using of self-made hot filament chemical vapor deposited (HFCVD) system. Positive bias voltage on the grid electrode on top of hot filaments and negative bias voltage on the substrate were applied. High purity and extremely smooth nanocrystalline diamond films were successfully prepared by using the double bias method. Raman, SEM, XRD and AFM results show that the diamond films obtained have grain sizes less than 20nm, nucleation density higher than 1011cm-1. The mechanism of double bias is also discussed in this paper. The positive grid bias increases the active, decomposition and ionization of hydrogen and methane molecules, while negative substrate bias helps positive carbon-containing ions bombard the substrate that leads to the high nucleation density of the diamond film.