As fluids approach their gas–liquid critical points, the physical properties such as the specific heat and compressibility diverge due to the formation of large molecular clusters. Incident light cannot penetrate near-critical fluids because of the large clusters, a phenomenon known as critical opalescence. In this paper, we irradiate near-critical carbon dioxide (ncCO2), the critical temperature and pressure of which are 31.0°C and 7.38 MPa, with a laser beam of 213, 266, 355 and 532 nm wavelength and show that CO2 is dissociated and particles are produced when the system is set so close to the critical point that critical opalescence occurs in the case of 213 and 266 nm wavelength, whereas no particles are produced when the temperature is made to deviate from the critical value. We also apply a dc electric field to ncCO2 during irradiation with a laser beam of 213 and 266 nm wavelength and find that particles are formed on both anode and cathode. As the intensity of the electric field increases, films are formed on the electrodes. Electron diffraction patterns and energy-dispersive x-ray, Auger electron, x-ray photoelectron and Raman spectroscopic analyses show that the particles and films are composed of amorphous carbon.