B–C–N compounds were prepared on molybdenum by means of bias-assisted hot filament chemical vapor deposition (HFCVD). Effect of the substrate temperature (Ts) on the growth of B–C–N films has been investigated systematically by x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) based on the detailed analysis and calculation of the XPS. The substrate temperature plays a key role in the formation of the bonding states, the composition, and the surface morphology. Boron carbonitride is the main phase at all depositing temperatures, and the obtained compounds are as follows: B0.83C0.17 + B0.39C0.35N0.26 at 873 K, B0.30C0.34N0.36 at 973 K, B0.64C0.36 + B0.51C0.23N0.26 at 1073 K, B0.51C0.31N0.18 at 1173 K, and B0.37C0.54N0.09 at 1273 K.