The work reports the study of the structure of carbon nanoparticles prepared by the pyrolysis of heliumdiluted acetylene under adiabatic compression in a piston reactor. At a pushing gas pressure of 0.5 MPa, 0.7 MPa, and 0.9 MPa the reaction gas was heated to temperatures of 400 °C, 600 °C, and 750 °C. By transmission electron microscopy it is found that carbon nanoparticles have a spherical shape and their size varies from 20 nm to 60 nm. The structural features of carbon nanoparticles are determined from the X-ray photoelectron spectroscopy data and the analysis of the near-edge X-ray absorption fine structure spectroscopy. Carbon nanoparticles prepared at a pushing gas pressure of 0.5 MPa have an amorphous structure and consist of hydrogenated carbon with impurities of polycyclic aromatic fragments. At a stronger compression ratio, carbon nanoparticles with a layered structure consisting mainly of sp2 hybridized carbon atoms are formed. The capacitance behavior and electrochemical impedance of carbon nanoparticle-based supercapacitors are compared.