Abstract: A one-step process for the synthesis of onion-like carbon nanoparticles is described. The process is based on a thermolysis of a NaN₃-C₆Cl₆ mixture. The effect of buffer gas (Ar or air) on the yield, morphology, and structure of the carbon products was investigated by electron microscopy, X-ray diffraction, and Raman spectroscopy. The products contained carbon-onions, amorphous carbon nanoparticles, and NaCl. The byproducts were completely removed using a simple purification process. The formation of onion-like nanoparticles is likely caused by a shock wave, a rapid increase of pressure, during thermolysis, which induced the coalescence of phenyl radicals.