This paper focuses on the synthesis of rhombohedral B4C (r-B4C) coatings by CO2 laser-assisted chemical vapour deposition (LCVD), using a dynamic reactive atmosphere of BCl3, H2 and CH4 or C2H4. The influence of the carbon precursor on the deposition kinetics is discussed. The use of ethylene as carbon precursor presents several advantages over the use of methane, which is the conventional carbon precursor in CVD processes. These advantages are mainly related to its high absorption coefficient at the laser wavelength and a higher sticking coefficient, which enables to attain higher deposition rates and film thickness control at lower carbon precursor concentration. Films with carbon content from 15 to 22 at.% were grown at a deposition rate as high as 0.12 µm s-1.