The system B-C-N contains the hardest known materials like diamond, cubic boron nitride and boron carbide, which also show excellent chemical resistance. The oxidation resistance is shifted to higher temperatures in comparison to pure diamond. But pure BCN coatings cannot be produced by conventional thermal spray processes, as the materials lack both a liquid phase and sufficient ductility to permit deposition. Conventional VPS equipment is successfully applied in Thermal Plasmajet CVD processes for high deposition rate synthesis of diamond coatings. The feasibility of SiCN or boron carbide synthesis by this method has also been proven. The use of liquid precursors results in outstanding deposition rates and improved operational safety. Methylized borazine is applied for synthesis of BCN coatings in thermal plasma jets. The use of single source precursors is advantageous with concern to the homogeneity of the coating forming species stoichiometry. For long-term storage cooling is necessary, but also under ambient conditions the precursor shows sufficient stability. Plasma gun nozzles with different diameter and design are applied and evaluated with concern to the resulting coating properties. Deposition rates of up to 1,500 µm/h have been achieved with homogeneous coating thickness and morphology on areas with 50 mm diameter. No porosity is detected in SEM investigations on cross sections and fracture surfaces show a fine columnar coating morphology. XRD investigations point at an amorphous structure. Only for very high substrate temperatures the formation of crystalline boron carbide B8C and h-BN or graphite phases is detected. Oxygen contamination results in boric acid formation and therefore has to be avoided carefully. During coating deposition on mild steel substrates the formation of boride and nitride reaction zones is observed. VPS sprayed nickel or molybdenum interlayers permit to inhibit the evolution of reaction zones. Thereby BCN coatings with thicknesses of up to 10 µm are deposited without local delamination. Space resolved emission spectroscopic analyses are carried out in order to detect coating forming and intermediate species. As Thermal Plasmajet CVD is a pure gas phase deposition process, the control of the space resolved emission permits easy process control.